US3425834A - Mordants for bleachable filter layers - Google Patents

Description

MORDANTS FOR BLEACHABLE FILTER LAYERS Filed Aug. 16, 1965 FIG GELAT/N CONTAIN/N6 SALT OF DYE AND 3-LAUROYLAMINO -I-- (N, N DIME THYL 3 *AMINO/PROP/OPHE NONE HYDRO- CHL ORIDE LIGHT-SENSITIVE SILVER HAL/DE EMULSION FILM SUPPORT LIGHT-SENSITIVE SILVER HAL/DE EMULSION DE LA TIN CON TA/NING SAL T OF DYE AND 3-LAUROYLAMINO (IV, N-DIME TH )L- 3 -AM/NO)PROPIOPHE NONE HYDRO CHL OR/DE FILM SUPPORT -BLUE-SENSITIVE SILVER HAL/DE EMULSION GELATIN CONTAIN/N6 SALT OF DYE AND 3-LAUROYLAMINO -/-(N, N-DIME THYL- S-AM/NOIPROP/OPHE NONE HYDROCHLORIDE r-GREEN-SENS/T/VE SILVER HAL/DE EMULSION 2O PRED-SENSITIVE SILVER HAL/DE EMULSION 2/ L FILM SUPPORT DUG'ALD A. BROOKS INVENTOR.

BY Dam/M ATTORNEY 8 AGENT United States Patent MORDANTS FOR BLEACHABLE FILTER LAYERS Dugald A. Brooks, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey Filed Aug. 16, 1965, Ser. No. 479,719

US. CI. 9684 Int. Cl. G03c 1/84 This invention relates to certain bulky, i.e., relatively high molecular weight, compounds that contain alkali cleavable, basic nitrogen groups such as alkylamino groups or nitrogen heterocyclic nuclei and function as alkalirelease mordants, to photographic materials, and more particularly to photographic elements containing these compounds in light-screening and light-absorbing layers, and to methods for their preparation.

The use of organic dye containing light-filter and lightabsorbing layers in photographic elements is well known as is the use of mordants which form substantially insoluble salts or otherwise react with water-soluble dyes, to render the dyes non-diffusing. Such dye-mordant lightscreening salt may be in a layer overlying a light-sensitive emulsion or overlying two or more light-sensitive emulsions; or it may be in a light-sensitive emulsion for the purpose of modifying a light record in such emulsion or for protecting an overlying light-sensitive emulsion or emulsions from the action of light of wavelengths absorbed by such light-screening substance, or it may be in a layer not containing a light-sensitive substance but arranged between two light-sensitive emulsions; or it may be in a layer serving as a backing on an element having one or more light-sensitive emulsions (for example, to reduce halation).

In particular, light-screening substances are often required (a) in overcoatings upon photographic elements to protect the light-sensitive emulsion or emulsions from the action of light which it is not desired to record, (b) in layers arranged between differentially color sensitized emulsions, e.g., to protect redand green-sensitive emulsions from the action of blue light, and (c) in backings forming the so-called antihalation layers on either side of a transparent support carrying the light-sensitive emulsion or emulsions.

In most cases and especially where the element contains a color sensitized emulsion or color sensitized emulsions, it is particularly desirable to employ light-screening substances which do not affect the generalsensitivity or the color sensitivity of light-sensitive emulsions with which they may come into contact. It is also particularly desirable to employ light-screening substances which do not substantially diffuse from the layers or coatings in which they are incorporated, either during the manufacture of the element or on storing it or in photographically processing it. Finally it is generally necessary to employ light-screening substances which can readily be rendered ineffective, i.e., decolorized or destroyed and removed prior to or during or after photographic processing. For many purposes it is particularly convenient to employ light-screening substances which are rendered ineffective by one of the photographic baths employed in processing the element after exposure, such as a photographic developing bath or fixing bath.

Numerous substances have been proposed as mordants to prepare the dye-mordant salts used as light-screening and light-absorbing materials for the purposes indicated above. Among the proposed mordants are relatively high molecular weight compounds having ionic charges opposite to those of the particular light-absorbing dye. For example, the dye employed might be an acid dye, in which case the mordant would be cationic. Typical of such proposed anordants are, for example, derived polymers such Claims ice as the basic reaction products of the polyvinylsulfonates and C-aminopyridines as described in D. D. Reynolds et al., US. Patents 2,701,243 and 2,768,078, granted Feb. 1, 1955, and Oct. 23, 1956, respectively. While polymeric mordants such as illustrated by the above-mentioned patents have the advantage of bulky molecules and do function to fix acid dyes in photographic layers, within their particular limitations, they have not been found entirely satisfactory in many applications primarily because these polymeric mordants on alkaline development do not tend to release the dye, still retain their mordanting property and, accordingly, not only tend to retain some residual dye as evidenced by background stain or coloration, but more importantly retain, i.e., fix, an appreciable amount of thiosulfate ion in the subsequent hypo processing used to remove unexposed silver halide. This results in relatively poor keeping qualities of the produced image. In view of this, it would be very desirable to have an effective mordant available that is free from such disadvantages.

I have now found that certain bulky or relatively high molecular weight compounds that contain alkali cleava'ble alkylamino groups or nitrogen heterocyclic nuclei are especially useful as precipitants and mordants for acid dyes in photographic layers, and that these compounds, moreover, satisfactorily overcome the above mentioned shortcomings of heretofore known mordants for this purpose. Thus, when incorporated in photographic layers, they function effectively as alkali-release mordants without retention of any residual dye or deleterious amounts of thiosulfate ion in the layers on processing, and the produced images are of very good quality and of outstanding keeping properties. These mordants are soluble in aqueous solutions, for example, dilute solutions of acids such as acetic, butyric, lauric, etc. acids. Furthermore, they readily form substantially non-diifusible salts with watersoluble dyes, and these are all compatible with various hydrophilic materials such as gelatin. In general, they have a molecular weight of at least 300.

It is, accordingly, an object of the invention to provide a photographic element having one or more layers containing at least one of the bulky basic nitrogen groups containing compounds or salts of the invention described above. Another object is to provide a backing layer containing at least one of these salts. Another object is to provide a light filter layer containing at least one of the above salts; which layer may be coated between two or more silver halide emulsion layers in a multilayer element. Another object is to provide an imbibition blank containing at least one of the above salts. Another object is to provide a light-sensitive gelatino-silver halide layer containing at least one of the above salts. Another object is to provide overcoating layers for photographic elements which contain at least one of the above salts. Another object is to provide a process for preparing the bulky nitrogen compounds and salts thereof. Other objects will become apparent from consideration of the description and the examples.

The bulky compounds that contain alkali cleavable alkylamino groups or nitrogen heterocyclic nuclei that are useful in the invention as alkali-release mordants include those represented by the following formula:

wherein n, g, and m each represent the same or different integers of from 1 to 2; R represents a lower alkyl (e.g., methyl, ethyl, butyl, etc.), alkoxy (e.g., methoxy, propoxy, butoxy, etc.), aryl (e.g., phenyl, tolyl, ethylphenyl, etc.), aryloxy (e.g., phenoxy, tolyloxy, ethylphenoxy, etc.), aralkyl (e.g., benzyl, phenethyl, etc.), etc.; R and R each represent the same or different members, such as,

hydrogen, an alkyl group having typically from 1 to 20 carbon atoms (e.g., methyl, propyl, isopropyl, dodecyl, phytyl, benzyl, phenethyl, etc.) or an aryl group (e.g., phenyl, dodecylphenyl, biphenyl, decyloxyphenyl, benzylphenyl, phenoxyphenyl, halophenyl, naphthyl, etc.); R represents an alkyl group having from 1 to 20 carbon atoms as described for R and an aryl group (e.g., phenyl, tolyl, octadecylphenyl, methoxyphenyl, dodecoxyphenyl, diphenyl, naphthyl, benzylphenyl, phenoxyphenyl, acetaminophenyl, propion-aminophenyl, laurylaminophenyl etc.); when n and g each represent the integer 1, R and R taken together represent a divalent alkylene group having from 3 to 4 carbon atoms in the chain and having the formula:

wherein i represents an integer of from 3 to 4; R represents hydrogen, an alkyl group having from 1 to 20 carbon atoms (e.g., methyl, decyl, octadecyl, phytyl, benzyl, tolylmethyl, phenethyl, etc.), and aryl (e.g., phenyl, tolyl, decylphenyl, octadecyloxyphenyl, =benzylpheny1, biphenyl, phenoxyphenyl, halophenyl, naphthyl, etc.); when m represents the integer 2, A represents a bifunctional group in which each of said functional groups is a substituted nitrogen atom having a valence with an odd number of from 3 to 5 with none of said substituents attached to the nitrogen being hydrogen, and when said nitrogen atom has a valence of 5, one of said substituents wherein R represents a lower alkyl group (e.g. methyl, ethyl, butyl, etc.); d represents an integer of from 2 to 6; X represents an acid anion (e.g., chloride, bromide, iodide, thiocyanate, sulfamate, perchlorate, methyl sulfate, ethyl sulfate, p-toluenesulfonate, etc.), and when m represents the integer 1, A represents a monofunctional group,

wherein R R and R each represent the same or different alkyl group (e.g., methyl, ethyl, decyl, etc.), and R and R taken together represent the nonmetallic atoms required to complete a 6-membered saturated heterocyclic nucleus (e.g., piperidino, morpholino, and N-su-bstituted piperazino (e.g., N-methylpiperazino, N-butylpiperizino, N-phenylpiperizino, etc.), X is as defined previously; R represents hydrogen, or a lower alkyl group (e.g., methyl, ethyl, etc.), each of said A groups having a molecular weight of less than 300; when monofunctional and less than 150 when bifunctional, Z represents the nonmetallic atoms required to complete an imidazoline nucleus; and Z represents the nonmetallic atoms required to complete a nucleus containing a heterocyclic ring having from 5 to 6 atoms, typical hetero atoms being nitrogen, oxygen, sulfur and selenium, Z representing particularly a thiazoline nucleus e. g., thiazoline, 4-methylthiazoline, 4-phenylthiazoline, S-methylthiazoline, S-phenylthiazoline, 4,5-dimethylthiazoline, 4,5-diphenylthiazoline,

4- (Z-thienyl) -thiazoline, etc.

a benzothiazoline nucleus (e.g., benzothiazoline, 4-chlorobenzothiazoline, S-chlorobenzothiazoline, -chlorobenzothiazoline, 7-chlorobenzothiazoline, 4-methylbenzothiazoline, S-methylbenzothiazoline, 6-methylbenzothiazoline, 5-bromobenzothiazoline, 6-bromobenzothiazoline, 4-phenylbenzolthiazoline, S-phenylbenzothiazoline, 4-methoxybenzothiazoline, 5-methoxybenzothiazoline, 6-methoxybenzothiazoline, S-iodobenzothiazoline, 6-iodobenzothiazoline, 4-ethoxybenzothiazoline, S-ethoxybenzothiazoline, tetrahydrobenzothiazoline, 5,6-dimethoxybenzothiazoline, 5,6-dioxymethylenebenzothiazoline, 5-hydroxybenzothiazoline, 6-hydroxybenzothiazoline, etc.), a naphthothiazoline nucleus e. g., a-naphthothiazoline, ,B-naphthothiazoline, S-methoxy-fi-naphthothiazoline, S-ethoxy-B-naphthothiazoline, 7-methoxy-a-naphthothiazoline, 8-methoXy-a-naphthothiazoline, etc. a thianaphtheno-7,6',4,S-thiazoline nucleus (e.g., 4'-methoXythianaphtheno-7',6',4,S-thiazoline, etc.), an oxazoline nucleus (e.g., 4-methylox-azoline, S-methyloxazoline, 4-phenyloxazoline, 4,5-diphenyloxazoline, 4-ethyloxazoline, 4,5-dimethyloxazoline,

5 -phenyloxazo1ine, etc.

a rbenzoxazoline nucleus (e.g., benzoxazoline, S-chlorobenzoxazoline, S-methylbenzoxazoline, S-phenylbenzoxazoline, 6-methylbenzoxazoline, 5,6-dimethylbenzoxazoline, 4,6-dimethylbenzoxazoline, S-methoxybenzoxazoline, S-ethoxybenzoxazoline, 6-chlorobenzoxazoline, 6-methoxybenzoxazoline, S-hydroxybenzoxazoline, 6-hydroxybenzoxazoline, etc.) a naphthoxazoline nucleus (e.g., a-n'aphthoxazoline, ,B,5-naphthoxazoline, ,B-naphthoxazoline, etc.-),

a selenazoline nucleus (e.g., 4-methylselenazoline, 4-phenylselenazoline, etc.),

a benzoselenazoline nucleus (e.g., benzoselenazoline, 5-chloroselenazoline, S-methoxyhenzoselenazoline, S-hydroxybenzoselen'azoline, tetrahydrobenzoselenazoline, etc. a naphthoselenazoline nucleus (e.g., a-naphthoselenazoline, 5,;3-naphthoselenazoline, fl-naphthoselen azoline, etc.

a thiazoline nucleus (e.g., thiazoline,

4-methylthiazoline, etc.), a 1,2,3,4-tetrahydroisoquinoline nucleus (e.g., l,2,3,4-tetrahydroisoquinoline, S-methyl-l,2,3,4-tetnahydroisoquinoline, S-methyl-1,2,3,4-tetrahydroisoquinoline, 6-chloro-1,2,3,4-tetrahydroisoquinoline, 6-methoxy-1,2,3,4-tetrahydroisoquinoline, 8-hydroxy-l,2,3,4-tetrahydroisoquinoline, etc.), a 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc. a l-substituted imidazoline nucleus (e.g., l-alkylimidazoline, 1-alkyl-4-phenylimidazoline, 1-alkyl-4,S-dimethylimidazoline, etc.), a l-substituted benzimidazoline nucleus (e.g., l-alkylbenzimidazoline, 1-aryl-5,6-dichlorobenzimidazoline, etc.), a l-substituted naphthimidazoline nucleus (e.g., 1-alkyl-u-naphthimidazoline, 1-aryl-fi-naphthimidazoline, 1-alkyl-5-methoxy-wnaphthimidazoline, etc.), a 1,2,4-thiadiazoline nucleus, a lor 4-alkyl-1,2,4-triazoline nucleus (e.g. l-methyl-1,2,4-triazoline, 1-butyl-1,2,4-triazoline, 4-ethyl-1,2,4-triazoline, etc.), a tetrazoline nucleus (e.g. tetrazoline, S-methyl-1,2,3,4-tetrazoline, 5-phenyl-1,2,3,4-tetrazoline, etc. and the like nuclei.

The components of Formula I above are so chosen as to give compounds having molecular weights in each instance of at least 150 for compounds derived from di-amines and 300 for compounds derived from monofunctional amines. Preferably, the compounds containing the -NR R groups are used in the form of their salts (e.g., the hydrochloride, the acetate, etc.) or in their quaternized forms, i.e., containing the group 5 -NR X\R1 wherein X, R R and R are as previously defined.

Included among the preferred mordants of Formula I are those having the formulas:

wherein p represents an integer of from 1 to 3, R R R R R and X are as defined previously and R represents the hydrogen atom, a straight or branched chain al-kyl group of from 1 to 22 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, octadecyl, etc.), an aryl group (e.g., phenyl, tolyl, naphthyl, etc.), an aralkyl group (e.g., benzyl, phenethyl, etc.), an alkoxy group (e.g., methoxy, ethoxy, butoxy, etc.) an aryloxy group (e.g., phenoxy, tolyloxy, naphthoxy, etc.), an alkoxyalkyl group (e.g., methoxymethyl, ethoxybutyl, isopropoxybutyl, butoxydodecyl, etc.), an acylamino group (e.g., acetamino, propionamino, butyrylamino, la-uroylamino, etc.).

In general my mordants of Formula I are produced by a Mannich reaction in which a ketone having the formula:

IV 0 O R. R1

R. O..tNH .-t( GH=t),. a.. in which R, R R 11 and g are as defined previously, is reacted with an aldehyde having the formula:

in which R is as defined previously and an amine (or amine salt) having one of the formulas;

wherein R R R X and a are as defined previously or XL Z R;HdI I-R in which R and Z have been defined previously and R represents an alkyl group having from 1 to 4 carbon atoms.

The mordants of Formula I in which m is 1 are produced advantageously by reacting compounds of Formulas IV, V, and VI or XI in mole ratios of about 1:1:1 respectively, while the compounds in which m is 2 are produced advantageously by reacting compounds of Formulas IV, V, and VII and VIII or IX or X in mole ratios of about 2:2:1 respectively.

The immediate reactions are advantageously carried out in a solvent such as glacial acetic acid and preferably at an elevated tmeperature, for example on a steam bath for several hours, the product then being precipitated by adding a nonsolvent (e.g., acetone), filtered out and recrystallized, for example, from absolute ethyl alcoholethyl acetate mixture. These compounds of Formula I may be quaternized by heating with a suitable quaternizing agent R7X wherein R and X are as previously defined (e.g., an alkyl halide, dialkyl sulfate, etc.) and these compounds are also effective alkali release mordants of the invention.

Illustrative ketones used to advantage include the following typical examples:

acetophenone lauroylaminoacetophenone decyl phenyl ketone ethyl phenyl ketone phenoxymethyl phenyl ketone phenethyl phenyl ketone benzyl phenyl ketone Z-butanone 2-octadecanone l-phenyl-octadecanone 2-phenyl cyclohexanone Z-benzyl cyclohexanone 2-octadecyl cyclohexanone 2-phenyl cyclopentanone 2-phytyl cyclopentanone Illustrative aldehydes used to advantage include formaldehyde, paraformaldehyde, acetaldchyde, benzaldehyde, etc.

Any monofunctional primary or secondary amine having a molecular weight of less than 300 or a bifunctional primary or secondary amine having a molecular weight of less than 150 can be used to advantage. Typical monofunctional amines includes the following:

aniline N-methylamine N-octadecylamine N,N-dibutylamine N,N-dimethylarnine N-methylaniline N-methylpiperazine morpholine piperidine thiazoline 1,2,3,4-tetrahydroisoquinoline Typical bifunctional amines include the following:

N,N'-dimethylpentamethylenedianiine N,N-dimethylethylenediamine imidazoline The following compounds will still further illustrate the mordants of Formula I.

Mordant No.: Name 1 3 lauroylamino 1 (N,N-dimcthyl-3- amino) propiophenone hydrochloride.

2 3 lauroylamino-l-(N,N,N-trimethyl-3- ammonium)propiophenone iodide.

3 3 dodecylphenylcarbamylcarbonylethyl-N,N-dimethylamine hydrochloride.

4 3 dodecylphenylcarbamylcarbonylethyl-N,N,Nirimethylammonium iodide.

5 3 laurylbenzoylethyl N,N dimethylamine hydrochloride.

6 3 laurylbenzoylethyl N,N,N trimcthylammoniurn iodide.

7 3 laurylbenzoylethyl N morpholine hydrochloride.

8 3 laurylbenzoylethyl N methyl N- morpholiniurn iodide.

9 1,4 bis(3 laurylbenzoylethyl)piperazine dihydrochloride.

10 1,4 bis(3 laurylbenzoylethyl)N,N'-dimethylpiperazinium diiodide.

11 3 decylbenzoylethylpiperidine hydrochloride.

12 3 decylbenzoylethyl N-methylpiperidinium iodide.

13 6 (N,N dimethylaminomethyl) 2- laurylcyclohexane hydrochloride.

14 6 (N,N,N,N tetramethylamrnonium)- 2-laurylcyclohexane iodide.

15 3 laurylbenzoyl 1 butenyl N,N-

dimethylarnine hydrochloride.

16 3 laurylbenzoyl 1 butenyl N,N,N-

trimethylammonium iodide.

17 3 laurylbenzoyl 3 butyl N,N dimethylamine hydrochloride.

1g 3 laurylbenzoyl 3 butyl N,N,N-trimethylammonium iodide.

19 3 octadecylbenzoyl 2 isopropyl-N,N-

dimethylamine hydrochloride.

20 3 octadecylbenzoyl-Z-isopropyl-N,N,N

trimethylammonium iodide.

21 3 phytylbenzoyl 1,2 diphenylethyl- N,N-dimethylarnine hydrochloride.

22 3 phytylbenzoyl 1,2 diphenylethyl- N,N,N-trimethylammonium iodide.

23 N methyl N,N bis(3 laurylbcnzoylethyl)amine hydrochloride.

24 N,N dimethyl N,N bis(3 laurylbenzoylethyl)ammonium iodide.

25 1,5 bis(3 laurylbenzoylcthyl) N,N- dimethylpentamethylene diamine dihydrochloride.

26 1,5 bis(3 laurylbenzoylethyl) N,N,

N,N' tetramethyl diammonium diiodide.

27 3 (3 laurylbenzoylethyl)benzothiazoline hydrochloride.

28 3 (3 laurylbenzoylethyl)benzothiazolinium iodide.

29 1,3 di(3 laurylbenzoylethyl)benzimidazoline dihydrochloride.

30 1,3 di(3 laurylbenzoylethyl)benzimidazolinium diiodide.

31 Phytyloylethyl N,N dimethylamine hydrochloride.

32 Phytyloylethyl N,N,N trimethylammonium iodide.

As previously mentioned, the above-defined mordants of the invention function as alkali-release mordants in photographic layers. Thus, under appropriate conditions of pH (i.e., alkaline conditions), they decompose to split or cleave the basic nitrogen fragment off of the bulky residue, and to lose their ability to act as mordants with release and subsequent removal of the mordanted dye from the system. A major advantage of the above alkalirelease mordants is, therefore, that the compounds do not retain either the previously mordanted dye or thiosulfate ion from the fixing bath, after processing, as do other compounds of similar mordanting ability.

The alkali cleavage reaction is illustrated with the structure of Formula IX above as follows:

wherein 12, R R R R and X are as previously defined.

The invention is further illustrated by the following examples describing the preparation and use of the mordanting compounds of the invention in photographic layers and elements.

Example 1.3-lauroylamino-1-(N,N-dimethyl-3- amino)propiophenone hydrochloride A mixture of 10 g. 3-1aurolya1ninoacetophenone (0.031 mole), 3.6 g. dimethylamine hydrochloride (0.044 mole), 2.5 g. paraformaldehyde (0.028 mole) in ml. glacial acetic acid was warmed on a steam bath for 3 hours. The dark red reaction mixture was reduced in volume under reduced pressure. Acetone was added to the concentrated solution. The resulting precipitate was collected and recrystallized from absolute ethanol-ethyl acetate, M.P. 1624.5 C.

The intermediate 3-1auroy1aminoacetophenone in the above reaction was prepared as follows:

A mixture of 20.0 g. m-aminoacetophenone (0.148 mole), approximately 10 g. sodium hydroxide and 200 ml. water was treated dropwise with 32.4 g. lauroyl chloride (0.148 mole) at room temperature. The resulting reaction mixture assumed a wax-like consistency. It was filtered and washed with water. The filtrate was neutralized with 6 N hydrochloric acid and the resulting solid collected. The collected portions were combined and dried, then recrystallized from benzene. The product was obtained as a white crystalline material, M.P. 87-895 C.

The above compound 3-lauroylamino-1-(N,N-dimethyl- 3-amino)propiophenone hydrochloride is an alkali cleavable Mannich base which can be decomposed in alkali splitting the basic nitrogen fragement off of the bulky residue. This compound, at a ratio of parts by weight to 1 part by weight of dye, mordanted the dye bis [3- methyLl-p-sulfophenyl 2 pyrazolin-5-one-(4)] pentamethineoxonol, in gelatin at a pH of 5.0, with no bleeding upon washing in water. The mordanted dye was partially bleached upon treatment of the coated gelatin layer (on a cellulose acetate film support) with a photographic developer having the composition:

p-Methylaminophenol sulfate g. 4.5

Sodium sulfite, desiccated g. 90.0 Hydroquinone g. 8.0 Sodium carbonate, monohydrated g. 52.5 Potassium bromide g. 5.0 WaterTo make liters 1.0

The bleaching was increased when the alkalinity of the developer was increased by the addition of sodium hydroxide. The residual yellow color was discharged by subsequent acidification of the gelatin layer. This was 10 mined, but none of the above samples bleached under these conditions. Thiosulfate retention values were determined by the Ross-Crabtree Method on unexposed film coatings, processed in a commercial Recordak processing machine.

EXAMPLE 2 Similar results are obtained by substituting for mordant No. 1 in Example 1 any of the specific illustrative mordants described previously herein. In each instance the dye being mordanted is held securely in its coated layer but upon photographic processing in the alkaline processing solutions the dye is completely released from the layer. The fragments into which the mordant is cleaved by alkali are not capable of and do not retain any dye or any thiosulfate ion in the processed photographic element.

The other odd-numbered mordants used to illustrate my invention are advantageously prepared by the Mannich condensation by processes Well known in .the art. Table 1 lists the ketone, aldehyde and amine salt used to make the mordants. Unless otherwise indicated, approximately equimolar amounts are used. The even-numbered mordants are made from the preceding odd-numbered mordants by treating it with methyl iodide.

Molrzdant Ketone Aldehyde Amine 3 Methyl3-dodecyl-1- Iaraiormaldehyde Dimethylamine hydrocarbamylphenyl ketone. chloride. 5 Methyl 3laurylphenyl ketone .do Do. I 7 "do do Morpholine hydrochloride. 9 Meghyl ii-laurylphenyl ketone Paratormaldehyde (2 moles) Piperazilnf dihydrochloride mo 8S [1 I110 B 11 Methyl 3decylphenul ketone Paraiormaldehyde Piperldine hydrochloride. 13 2-laurylcyclohexanone do Dimetliiylarnine hydrochlor de. 15 Allyl 3-la;urylphenyl ketone do Do. 17 Propyl 3-laurylphenyl ketone do Do. 19 Mletltiyl3-octadecylphenyl Aeetaldehyde Do.

'e one. 21 Benzyl S-phytylphenyl ketone. Benzaldehyde Do. 23 Methyl 3-laurylphenyl ketone Paraiormaldehyde (2 moles) Methylamine hydroe (2 moles). chloride (1 m e 25 do ..do 1.5-dimethyl pentamethylene diamine. 27 Methyl 3-laurylphenyl ketone... Paralonnaldohyde Benzothiazoline hydrochloride. 29 Methyl 3-laurylphenyl ketone Paraformaldehyde (2 moles) Benzimidazoline dihydro- (2 moles). chloride (1 mole). 31 Methyl phytylketone Paraformaldehyde Dimethylamine'hydro' chloride.

then treated with a fixing bath of the following com 45 Still more typical mordants of my invention are the position: following: i thlosulfate MO -dam; N NaIne si deslccated 48 33 6-(N,Ndimethylaminornethyl)-2-phenyl- Aceilc s 2 i 7 5 r cyclohexanone hydrochloride, Bone acid, crystals 00 34 6-(N,N-diethylarninomethyl)-2-tolyl-cyc1o- Potasslum 211ml t '0 hexanone hydrochloride. WateF-T0 ma 6 11 35 N,N-dibutylaminomethylcyclopentanone Result:Mordanted well. Bleached effectively in the hydrochlor de.

developer. Retained no hypo from the fixing bath. 36 -p y y The above results for Example 1 were made for hand 55 ethyl)hydrochloride.

coatings on cellulose acetate film support, the melts for which were prepared as follows:

To 10 cc. of 10% photographic gelatin melted at 40 C. was added 30 or rngs. of mordant dissolved in 10 cc. of the appropriate solvent. The pH of the solution was adjusted to 4.5-5.0 with glacial acetic acid. To this was then added 10 mgs. of bis[3-methyl-l-p-shlfophenyl-S- pyraZolone-(4)]pentamethineoxonol dissolved in the appropr-iate solvent with vigorous stirring. The pH of the melt was then readjusted to 6.0 01 with.2.5 N NaOH, a coating aid added, the total volume adjusted to 32 cc. with distilled water and the melt coated and dried.

The bleed test consisted of immersinga portion of the hand coating in stagnant, distilled water at 75 F. for 2 minutes and inspecting for signs of dye bleeding out of the gel layer. If no bleeding was detected, the immersion was repeated for another 2 minute interval. Bleachability was determined by immersing a portion of the hand coating in the developer for 2 minutes and observing the loss in color. Bleachability in the fixing bath was also deter- These and the other mordants of my invention are prepared according to the procedures described previously. Blicke in Chapter 10 of Organic Reactions, Volume 1, published by Wiley, describes the Mannich condensation reaction.

The photographic elements prepared with the abovedescribed mordants of the invention comprise a support material having thereon at least one hydrophilic colloid layer containing a mordant of the invention, which layer may also contain a light-sensitive silver halide. However, the preferred light-sensitive photographic elements, comprise a support having thereon at least one hydrophilic colloid layer containing a mordant of the invention and at least one light sensitive silver halide emulsionlayer. The mordant containing light-screening and antihalation layers are customarily prepared by coating on the support or photographic elements by methods well known in the art, a water solution comprising at least one mordant of the invention, an acid dye, a water-permeable hydrophilic colloid binder and a coating aid such as saponin. For most purposes, it is also desirable to add agents to harden the colloidal binder material so that the light-screening layer will remain intact in the photographic element during and following the processing operations. The pH of the coating solution is adjusted when necessary to a level that is compatible with the light-sensitive emulsion layer by the usual methods. The proportions of mordant, dye, colloidal binder, hardener and coating aid may be varied over wide ranges and will depend upon the specific requirement of the photographic element being produced. The methods used to determine the optimum compositions are well known in the art and require no further elucidation here. Suitable support materials include any of those used in photography such as cellulose acetate, cellulose propionate, cellulose acetate-butyrate, cellulose nitrate, synthetic resins such as nylon, polyesters, polystyrene, polypropylene, etc., paper, and the like.

Suitable hydrophilic colloid materials that can be used in the mordant containing compositions and layers, and photographic elements, of the invention include gelatin, albumin, collodion, gum arabic, agar-agar, cellulose derivatives such as alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in U.S. Patent 2,949,442, issued Aug. 16, 1960, polyvinyl alcohol, polyvinyl pyrrolidone, and others well known in the art. The above-mentioned amphoteric copolymers are made by polymerizing the monomer having the formula:

| COOH wherein R has the above-mentioned meaning, such as an alkylamine salt. These monomers can further be polymerized with a third unsaturated monomer in an amount up to about 20%, and preferably from -15%, of the total weight of monomer used, such as an ethylene monomer that is copolymerizable with the two principal monomers. The third monomer may contain either a basic group or an acid group and may, for example, be vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, acrylates, methacrylates, acrylamide, methacrylamide, etc. Examples of these polymeric gelatin substitutes are copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acrylamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; the copolymers of allylamine, acrylic acid and styrene; the copolymers of allylamine, methacrylic acid and acrylonitrile; etc.

The dyes that can be effectively mordanted in accordance with my invention include any filter dye that has one or more acidic group substituents such as sulfo or carboxyl groups, including for example, the oxonol dyes described and claimed in copending application of Joseph Bailey, Ser. No. 98,709, filed Mar. 27, 1961, now Patent No. 3,247,127; having the formula:

and more particularly the dyes of the formula:

12 wherein Z represents the nonmetallic :atoms necessary to complete a 1-carboxyalkyl-3-hydrocarbon substituted hexahydro-2,4,6-trioxo-5-pyrimidine nucleus, n in each case is an integer of from 1 to 3, each R represents a carboxy- -alkyl group in which the carboxy substituent is attached to an :alkyl group having from 1 to 2 carbon atoms, R is an alkyl group of from 1 to 8 carbon atoms or an aryl group such as phenyl or an alkyl or alk-oxy substituted phenyl group, and X is hydrogen or an alkyl group of from 1 to 4 carbon atoms, such that no more than one X" is an alkyl group. Other suitable acid dyes include the benzoxazole-pyrazolone merocyanine dyes described in copending application of Jones et al. U.S. Ser. No. 167,666, filed Jan. 22, 1962, now Patent No. 3,282,699, having the formula:

wherein R represents :an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, etc., or a carboxyalkyl group, such as carboxymethyl, carboxyethyl, carboxypropyl, etc., or a sulfoalkyl group, such as sulfoethyl, sulfopropyl, sulfobutyl, etc.; Z represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series (including benzoxazole and benzoxazole substituted with substitutions such as methyl, ethyl, phenyl, methoxy, ethoxy, chlorine, bromine, etc.) or a nucleus of the benzoxazole series which has a sulfo-substituent on the benzene ring as well as one or more of the above-mentioned simple substituents, such that when R represents an alkyl group, Z" represents the sulfo-substituted benzoxazole nucleus and when R, represents a carboxyalkyl group or a sulfoalkyl group, Z" represents the nonmetallic atoms necessary to complete a benzoxazole nucleus; Q represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the suitephenyl pyrazolinone series and n is an integer from 1 to 3. However, the invention is not limited to just those dyes coming within the general formulas of the above-mentioned copending applications, since as previously set forth any filter dye containing one or more sulfo or carboxyl groups can be employed, for example, the yellow dyes mentioned in Mader et al. U.S. Patent 3,016,306, issued Jan. 9, 1962, columns 5 and 6.

Typical light-filtering dyes include, for example,

bis( 1-butyl-3 -carboxymethylhexahydro-2,4,6-trioxo-5- pyrimidine pentamethineoxonol,

bis( 1-carboxymethyl-3-cyclohexylhexahydro-2,4,6-trioxo- 5 pyrimidine pentamethineoxonol,

bis 1-butyl-3-carboxymethylhexahydro-2,4,6-triox0-S pyrimidine) trimethineoxonol,

bis( 1-carboxymethylhexahydro-3 -octyl-2,4,6-trioxo-S- pyrimidine) met-hineoxonol,

4-[ (3-ethyl-2 3H -benzoxazolylidine ethylidene] -3 methyl- 1- p-sulfophenyl) -2-pyrazolin-5-one monosulfonated,

4- 4- (3 -ethyl-2 3H -benzoxazoylidene) -2-butenylidene] 3-methyl-1- (p-sulfophenyl) -2-pyrazolin-5-one monosulfonated,

4[ (3-B-carboxyethyl-2 3H -benzox azolylidene ethylidene] -3-methyl- 1- p-sulfophenyl -2-pyrazolin-5-one,

4- [4- (3 -fi-carboxyethyl-2 (3H) -benzoxazolylidene)-2- butenylidene] -3-methyll- (p-sulfophenyl) -2-pyrazolin- S-one,

bis(1-butyl-3 -carboxymethyl-S-barbituric acid) trimethine oxonol,

bis(1-butyl-3 -carboxymethyl-S-barbituric acid pent-amethineoxonol,

bis 3-methyl- 1- (p-sulfophenyl) -2-pyrazolin-5-one (4) methineoxonol,

bis 3 -methyl-1- p-sulfophenyl -2-pyrazolin-5 -one (4) trimethineoxonol,

bis 3 -methyl-1- p-sulfophenyl -2-pyrazolin-5 -one-( 4) pentamethineoxonol,

bis 3-methyl-1- (p-sulfophenyl -5-pyrazolone-(4)] pentamethineoxonol, and

13 typical ultraviolet absorbing dyes include the 2,5-bis(substituted sulfophenyl)thiazolo[5,4-d]thiazole disodium salts of Sawdey U .S. Ser. 183,417 filed Mar. 29, 1962, such as 2,5 -bis o-methoxy-x-sulfophenyl thiazolo ,4-d] thiazole disodium salt,

2,5-bis (o-hexyloxy-x-sulfophenyl)thiazolo[5,4-d]

thiazole disodium salt,

2,5-bis(o-decyloxy- -sulfophenyl)thiazolo[5,4-d] thiazole disodium salt,

2,5 -bis (o-methyl-x-sulfophenyl) thiazolo [5,4-d] thi-azole disodium salt,

2,5 -bis 5 -butyl-Z-methyl-x-sulfophenyl) thiazolo[5 ,4-d]

thiazole disodium salt,

2,5 -bis m-methyl-x-sulfo phenyl thiazolo [5 ,4-d] thiazole disodium salt,

2,5-bis p-propyl-x-sulfophenyl) thiazolo [5 ,4-d] thiazole disodium salt, etc.;

the ultraviolet absorbing dyes of Sawdey US. Patent 2,739,888, issued Mar. 27, 1956, such as 3-phenyl-2-phenylimino-5-o-sulfobenzal-4-thiazolidone sodium salt,

5- 4-methoxy-3 -sulfob enzal -3 -phenyl-2-phenylimino-4- thiazolidone (sodium salt),

3-phenyl-2-phenylimino-5-[3-(3-sulfobenzamido)benza1]- 4-thiazolidone (sodium salt),

3-benzyl-2-phenylimino-5-o-sulfobeuzal-4-thiazolidone (sodium salt),

5 2,4-dicarb oxymethoxyb enzal) -3-phenyl-2-phenylimino- 4-thiazolidone sodium salt, etc.,

tartrazine, and the like filter dyes.

Hardening materials that may be used to advantage include such hardening agents as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in White US. Patent 2,080,019, issued May 11, 1937, a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7-octene'-2,3,5, 6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll U.S. Patents 2,725,294, and 2,725,295, both issued Nov. 29, 1955; a cyclic 1,2-diketone such as cyclopentane-1,2-dione as described in Allen and Byers US. Patent 2,725,305, issued Nov. 29, 1955; a bisester of methane-sulfonic acid such as 1,2-di(methanesulfonoxy) ethane as described in Allen and Laakso US. Patent 2,726,162, issued Dec. 6, 1955; 1,3-dihydroxymethylbenzirnidazol-Z-one as described in July, Knott and Pollak, US. Patent 2,732,316, issued J an. 4, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as B- methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness, Canadian Patent 588,451, issued Dec. 8, 1959; a bis-aziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as described in Allen and Webster US. Patent 2,950,197, issued Aug. 23, 1960; or 2,3-dihydroxydioxane as described in Jeffreys US. Patent 2,870,013, issued Jan. 20, 1959.

The photognaphic element utilizing my light-screening layers have light-sensitive emulsion layers containing silver chloride, silver bromide, silver chlorobromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material. Any light-sensitive silver halide emulsion layers may be used in these photographic elements. The silver halide emulsion may be sensitized by any of the sensitizers commonly used to produce the desired sensitometric characteristics.

In the accompanying drawing which further illustrates the preferred photographic elements of my invention:

FIG. 1 shows light-screening layer 10 comprising gelatin, an acid substituted filter dye and the mordant of Example 1 coated over a light-sensitive silver halid emulsion layer 11 which is coated on support 12.

FIG. 2 shows antihalation layer 15 comprising gelatin, an acid substituted dye and the mordant of Example 1,

coated adjacent to support '16 and a light-sensitive silver halide emulsion layer 14 coated over layer 15.

FIG. 3 shows a multilayer color element comprising a support 21 having a red-sensitive silver halide emulsion layer 20 coated thereon, a green-sensitive silver halide emulsion layer 19 coated over layer 20, a light-screening layer 18 comprising gelatin, an acid substituted dye, and the mordant of Example 1 coated over layer 19, and a blue-sensitive silver halide emulsion layer 17 coated over layer 18.

The use of my alkali-release mordants in light-screening layers over light-sensitive silver halide emulsion layers, and in antihalation undercoat layers, to produce improved photographic elements has been illustrated in the preceding examples. However, it will be apparent that the mordants of the invention can also be advantageously used in light-screening layers between two or more color sensitized silver halide emulsion layers, or in antihalation backing layers, or incorporated directly in light-sensitive silver halide emulsion layers, or they can be used to prepare imbibition dye trapsfer blanks of improved properties.

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

I claim:

1. A photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one mordant represented by the formula:

wherein n represents an integer of from 1 to 2; g represents an integer of from 1 to 2; m1 represents an integer of from 1 to 2; R represents a member selected from the class consisting of a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group and an aralkyl group; R represents a member selected from the class consisting of hydrogen, an alkyl group, an aryl group, and when taken together with the R group represents a divalent alkylene group having the formula:

wherein j represents an integer of from 3 to 4; R represents a member selected from the class consisting of an alkyl group, an aryl group and when taken together with the R group represents the said divalent alkylene group, such that when R and R are taken together to form said divalent alkylene group, n and g each represent the integer 1; R represents a member selected from the class consisting of hydrogen, an alkyl group and an aryl group; R represents a member selected from the class consisting of hydrogen, an alkyl group and an aryl group; when m represents the integer 2, A represents a bifunctional group having a molecular weight less than in which each of the said functional groups is a substituted nitrogen atom having a valence with an odd number of from 3 to 5 with none of the said substituents attached to nitrogen being hydrogen, and when the nitrogen atoms have a valence of 5, one of said substituents on each of said nitrogen atoms is an acid anion, and when m represents the integer 1, A represents a substituted nitrogen having a valence having an odd number of from 3 to 5 with none of said substituents attached to nitrogen being hydrogen, and when the nitrogen atom has a valence of 5, one of said substituents on the said nitrogen is an acid anion, said A group having a molecular weight of less than 300, said element containing silver halide.

1 2. A photographic element of claim 1 in which when m is the integer 2, A represents a group selected from the class consisting of N group, a-N N- group and a N group Z X Z X R5 wherein R represents a lower alkyl group; d represents an integer of from 2 to 6; X represents an acid anion; Z represents the nonmetallic atoms required to complete a nucleus selected from the class consisting of an imidazoline nucleus, a benzimidazoline nucleus and a naphthimidazoline nucleus; R represents a group selected from the class consisting of an alkyl group, and an aryl group; and when m is the integer l, A represents a group selected from the class consisting of group, aN-R group and a NCHRB group R6 X R7 wherein R R and R each represents an alkyl group, and together R and R represent the nonmetallic atoms required to complete a group selected from the class consisting of piperidine, N-substituted piperazine, and morpholine; R represents a member selected from the group consisting of hydrogen, and a lower alkyl group; X represents an acid anion and Z represents the nonmetallic atoms required to complete a heterocyclic nucleus having from 5 to 6 members in the ring.

3. A photographic element of claim 1 in which when m is the integer 2, A represents a group selected from the class consisting of V aN a N N- group /I CHZ-CHZ X CH2 R4 OH: R;

R /R Z a N group, a NR group and a N CHR group R, X B

wherein R R and R each represents an alkyl group, and together R and R represent the nonmetallic atoms required to complete a group selected from the class consisting of piperidine, N-substituted piperazine, and morpholine; R represents a member selected from the group consisting of hydrogen, and a lower alkyl group; X represents an acid anion and Z represents the nonmetallic atoms required to complete a heterocyclic nucleus having from 5 to 6 members in the ring selected from the class consisting of a thiazoline nucleus, a benzothiazoline nucleus, a naphthothiazoline nucleus, a thianaphtheno-7,6',4,S-thiazoline nucleus, an oxazoline nucleus, a benzoxazoline nucleus, a naphthoxazoline nucleus, a selenazoline nucleus, a benzoselenazoline nucleus, a naphthoselenazoline nucleus, a thiazoline nucleus, at 1,2, 3,4-tetrahydroisoquinoline nucleus, a 3,3-dialkylindolenine nucleus, an imidazoline nucleus, a benzimidazoline nucleus, and a naphthimidazoline nucleus.

4. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer container at least one substantially nonditfusible salt of a water-soluble acid dye with a compound represented by the formula:

wherein p represents an integer of from 1 to 3; R and R each represents an alkyl group, R and R taken together represent the nonmetallic atoms required to complete a group selected from the class consisting of piperidine, N-substituted piperazine and morpholine; and R represents a member selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxyalkyl group, and an acylamino group; said compound having a molecular weight of at least 300, said element containing silver halide.

5. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nonditfusible salt of a water-soluble acid dye with a compound represented by the formula:

( lah:

wherein p represents an integer of from 1 to 3, R R and R each represents an alkyl group, R and R taken together represent the nonmetallic atoms required to complete a group selected from the class consisting of piperidine, N-substituted piperazine and morpholine; R represents a member selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxyalkyl group, and an acylamino group; and X represents an acid anion; said compound having a molecular weight of at least 300, said element containing silver halide.

6. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nondiffusible salt of a water-soluble acid dye with 3-lauroylaminol- (N,N-dimethyl-3-amino propiophenone hydrochloride, said element containing silver halide.

7. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nondifiusible salt of a water-soluble acid dye with 3-dodecylphenylcarbamylcarbonylethyl N,N dimethylamine hydrochloride, said element containing silver halide.

8. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nondilfusible salt of a water-soluble acid dye with 3-laurylbenzoylethyl- N-methyl-N-morpholinium iodide, said element containing silver halide.

9. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nondiffusible salt of a water-soluble acid dye with 1,4-bis(3-laurylbenzoylethyl)-N,N-dimethylpiperazinium diiodide, said element containing silver halide.

10. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nondiffusible salt of a water-soluble acid dye with 6-(N,N-dimethylaminomethyl)-2-laury1cyclohexane hydrochloride, said element containing silver halide.

11. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nondifrusible salt of a watersoluble acid dye with N-methyl-N,N-bis (3-laurylbenzoylethyl)amine hydrochloride, said element containing silver halide.

12. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least'one substantially nondifiusible salt of a Water-soluble acid dye with 1,5-bis(3-laurylbenzoylethyl) N,N'-dimethylpentamethylenediamine dihydrochloride, said element containing silver halide.

13. A light-sensitive photographic element comprising a support material having thereon a 'hydrophilic colloid layer containing at least one substantially nondilfusible salt of a water-soluble acid dye with l,3-di(3-laurylbenzoylethyl)benzimidazolinium diiodide, said element containing silver halide.

14. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially nondiffusible salt of a water-soluble acid dye with phytylethyl-N,N,N- trimethyl ammonium iodide, said element containing silver halide.

15. An element comprising a support material having thereon a hydrophilic colloid layer containing at least one salt of an acid dye and a mordant represented by the formula:

wherein represents an integer of from 3 to 4; R represents an integer of from 1 to 2; m represents an integer of from 1 to 2; R represents a member selected from the class consisting of a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group and an aralkyl group; R represents a member selected from the class consisting of hydrogen, an alkyl group, an aryl group, and when taken together with the R group represents a divalent alkylene group having the formula:

-([JH(CH2) -1 wherein i represents an integer from 3 to 4; R represents a member selected from the class consisting of an alkyl group, an aryl group and when taken together with the R group represents the said divalent alkylene group, such that when R and R are taken together to form said divalent alkylene group, n and g each represent the integer 1; R represents a member selected from the class consisting of hydrogen, an alkyl group and an aryl group; R represents a member selected from the class consisting of hydrogen, an alkyl group and an aryl group; when m represents the integer 2, A represents a bifunctional group having a molecular weight less than in which each of said functional groups is a substituted nitrogen atom having a valence with an odd number of from 3 to 5 with none of the said substituents attached to nitrogen being hydrogen, and when the nitrogen atoms have a valence of 5, one of said substituents o neach of said nitrogen atoms is an acid anion, and when m represents the integer 1, A represents a substituted nitrogen having a valence having an odd number of from 3 to 5 with none of said substituents attached to nitrogen being hydrogen, and when the nitrogen atom has a valence of 5, one of said substituents on said nitrogen is an acid anion, said A group having a molecular weight of less than 300, said element containing silver halide.

UNITED STATES PATENT OFFICE Patent No.

834 February 4 1969 Dugald A. Brooks It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 15, lines 44 through 47, the right-hand formula should appear as shown below:

Column 16, lines l9 p Column 17, lines lines 44 and 45 R represents an "o neach" should 38 through 43, that part of the formula reading should read 39 through 43 that part of the formula reading 3 should read (-CH=C)g cancel "j represents an integer of from 3 to 4 integer of from 1 to Z Column 18, line 26 read on each Signed and sealed this 15th day of September 1970 (SEAL) Attest:

EDWARD M.FLETCHER,JR. Attesting Officer WILLIAM E. SCHUYLER, Commissioner of Paten

Claims (1)

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT MATERIAL HAVING THEREON A HYDROPHILIC COLLOID LAYER CONTAINING AT LEAST ONE MORDANT REPRESENTED BY THE FORMULA:

Images