US3438779A - Mordants for bleachable filter layers - Google Patents

Description

April 15, 1969 :5. w. HESELTINE ET AL ,438,

MORDANTS FOR BLEACHABLE FILTER LAYERS Filed Aug. 16, 1965 GELAT/N CON TAIN/NG SALT 0F DYE AND /,6 -HEXAME THYLE NE BIS! N-Z-ME TH YL-4, 6 'D/PHEN YLPYR/D/N/UM I OD/DE --LIGHT SENSITIVE SILVER HAL/DE EMULSION I 2" FILM sup/ om LI GHT-SENSITIVE SILVER HAL/DE EMULSION GELA TIN CONTAINING SALT OF DYE AND I, S-HEXAME TH YLE NE BIS (N -2 -ME TH YL- 4, 6 -D/PHE N YL PYR/DIN/UM I OD/DE FIG 3 BLUE-SENSITIVE SILVER HAL/DE EMULSION GEL A TIN CONTAIN/N6 SAL T OF DYE AND l,6-HEXAMETH YLENE -BIS (N 2- METHYL -4, 6 -D/PHENYLPYR/D/N/UM IOD/DE GREEN-SENSITIVE SILVER HAL/DE EMULSION RED-SENSITIVE SILVER HAL/DE EMULSION F FILM SUPPORT DONALD W. HESELT/NE DUGALD A. EROOKS INVENTORS BY IRMM RQMW A TTORNEY 8 AGENT United States Patent (lfice 3,438,779 Patented Apr. 15, 1969 3,438,779 MORDANTS FOR BLEACHABLE FILTER LAYERS Donald W. Heseltine and Dugald A. Brooks Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Aug. 16, 1965, Ser. No. 479,718

Int. Cl. G03c 1/84 US. Cl. 96-84 11 Claims ABSTRACT OF THE DISCLOSURE A bulky quaternary nitrogen heterocyclic alkali-release mordant that forms a methylene base under alkaline conditions with loss of the positive charge on the nitrogen atoms and the corresponding loss in ability to mordant anions, is advantageously used as a mordant for acid dyes in a hydrophilic colloid layer, especially in a hydrophilic colloid light-absorbing or light-filtering layer of a photographic element where it is desired to firmly mordant an acid dye in the photographic element until photographic processing when it is desired to completely release the acid dye without remordanting dye or thiosulfate ions from the fixing bath.

This invention relates to certain bulky, i.e., relatively high molecular weight, quaternary nitrogen heterocyclic compounds which function as alkali-release mordants, to photographic materials and more particularly to photographic elements containing these compounds in lightscreening 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 general sensitivity 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 lightscreening substances which are rendered ineffective by oneof 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 a cationic compound. Typical of such proposed mordants are, for example, derived polymers such as the basic reaction products of 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, so they 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 quality and stability 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.

We have now found that certain bulky quaternary nitrogen heterocyclic compounds 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 thiosul-fate 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-diffusing salts with water-soluble dyes, and these are all compatible with various hydrophilic materials such as gelatin. They are compounds of definite constitution and, in general, have molecular weights of about at least 300.

It is, accordingly, an object of the invention to pro vide a photographic element having one or more layers containing at least one of the bulky nitrogen heterocyclic 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 quaternary nitrogen heterocyclic compounds and salts thereof. Other objects will become apparent from consideration of the description and the examples.

The bulky quaternary nitrogen heterocyclic compounds of the invention that are useful as alkali-release mordants include those represented by the following general formula:

wherein m and 11 each represents an integer of from 1 to 2, R and R each represents the hydrogen atom, an alkyl group of from 1 to 18 carbon atoms and preferably a lower alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, octadecyl, benzyl, phenethyl, etc.), or an aryl group (e.g., phenyl, tolyl, naphthyl, etc., and preferably phenyl), R represents a divalent alkylene group containing up to about 18 carbon atoms in the chain (e.g., methylene, ethylene, propylene, 1,2-propylene, butylene, hexatmethylene, decamethylene, octadecamethylene, Xylylene, etc.) or a divalent arylene group (e.g., p-phenylene, m-phenylene, a tolylene group, etc.), X represents an acid anion (e.g., chloride, bromide, iodide, thiocyanate, sulfamate, perchlorate, methyl sulfate, ethyl, sulfate, p-toluenesulfonate, etc.), and Z and Z each represents the nonmetallic atoms required to complete a nucleus containing a heterocyclic ring having to 6 atoms in the ring typically having nitrogen, oxygen, sulfur and selenium as the hetero atoms, typical nuclei include a thiazole nucleus (e.g., thiazole,

4-methyl-thiazole,

4-phenylthiazole,

S-methylthiazole,

S-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole, etc.),

a benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazo1e, 7-chlor0benzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, S-bromobenzothiazole, 6-bro.mobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, S-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.

a naphthothiazole nucleus (e.g., a-naphthothiazole, ,8-naphthothiazole, S-methoxy-fi-naphthothiazole, 5-ethoxy-B-naphthothiazole, 7-methoxy-a-naphthothiazole, 8-methoXy-u-naphthothiazole, etc. a thianaphtheno-7',6',4,5-thiazole nucleus, (e.g., 4-methoxythianaphtheno-7,6',4,5-thiazole, etc.), an oxazole nucleus (e.g., 4-rnethyloxazole, S-methyloxazole,

4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole, etc.

a benzoxazole nucleus (e.g., benzoxazole, S-chlorobenzoxazole, S-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, 5-ethoxybenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc. a naphthoxazole nucleus (e.g., ot-naphthoxazole, [Lfl-naphthoxazole, fl-naphthoxazole, etc.

a selenazole nucleus (e.g., 4-methylselenazole, 4-phenylselenazole, etc.),

a benzoselenazole nucleus (e.g., benzoselenazole, 5-chloroselenazole, 5-methoxybenzoselenazole, S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.) a naphthoselenazole nucleus (e.g., ot-naphthoselenazole, fifi-naphthoselenazole, B-naphthoselenazole, etc.),

a thiazolin nucleus (e.g., thiazoline, 4-methylthiazoline, etc.),

a quinoline nucleus (e.g., quinoline, 3-methylquinoline, S-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.

an isoquinoline nucleus (e.g., isoquinoline, B-methylisoquinoline, S-methylisoquinoline, 6-chloroisoquinoline, 6-methoxyisoquinoline, S-hydroxyisoquinoline, etc.), a 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethy1indolenine, 3,3,S-trimethylindolenine, 3,3,7-trimethylindolenine, etc. a pyridine nucleus (e.g., pyridine,

4-methylpyridine, 6-methylpyridine, 4,6-dimethylpyridine, 4-butylpyridine, 4-decylpyridine, 4-octadecylpyridine, 4,6-dibutylpyridine, 4-benzylpyridine, 6-benzylpyridine, 4-phenylpyridine, 4,6-diphenylpyridine, 4,6-dinaphthy1pyridine,

4-(2,thienyl) pyridine, 6-(2-thienyl) pyridine, 4,6-di(2-thienyl)-pyridine,

4- (2-pyrryl pyridine,

4-(2-indolyl)pyridine, 4-(3-indolyl)pyridine,

4- 3-pyridyl pyridine, 4-(4-pyridyl)pyridine, 4,6-di(2-pyrryl) pyridine, 4-phenoxypyridine, 4-alkoxypyridines, 6-alkoxypyridines, 4,6-dialkoxypyridines, 4-(2-furyl)pyridine, etc.),

an imidazole nucleus (e.g., imidazole,

l-alkylimidazole, l-alkyl-4-penylimidazole, 1-alkyl-4,5-dimethylimidazole, etc.), a benzimidazole nucleus (e.g., benzimidazole, l-alkylbenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, etc. a naphthimidazole nucleus (e.g., 1-alkyl-a-naphthimidazole, 1-aryl-fl-naphthimidazole, 1-alkyl-5-methoxy-u-naphthimidazole, etc. a thiazole nucleus (e.g.,

a 1,2,4-thiadiazole),

an oxadiazole nucleus (e.g., 1,2,4-oxadiazole,

l,3,4oxadiazole, etc.),

a l or 4 alkyl-1,2,4-triazole nucleus (e.g., l-methyl-l,2,4-triazole, l-butyl-l,2,4triazole,

4-ethyl- 1,2,4-triazole, etc.

a tetrazole nucleus (e.g.,

tetrazole,

S-methyl-1,2,3,4-tetrazole,

S-phenyll ,2,3,4-tetrazole, 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 300.

More particularly, the bulky quaternary nitrogen heterocyclic compounds of the invention that are especially suitable as alkali-release mordant in photographic layers include those represented by the following general formula;

wherein d represents an integer of from 1 to 3, 2 represents an integer of from 1 to 18, R and R are as previously defined with the -CHR R groups being substituted on a carbon atom in the 2 or 4 position in the pyridinium rings, R represents the hydrogen atom and a lower alkyl group (e.g., methyl, ethyl, etc.), R represents the hydrogen atom, a halogen atom (e.g., bromine, chlorine, etc.), a straight or branched chain alkyl 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 alkoxy alkyl group (e.g., methoxymethyl, ethoxybutyl, isopropoxybutyl, butoxydodecyl, etc.), or a heterocyclic nucleus (e.g., Z-thienyl, 2-pyrryl, 2-indolyl, 3-indolyl, Z-furyl, 3-pyridyl, 4-pyridyl, etc.), such that stance of at least 300.

To prepare the preferred compounds of the invention coming under Formula II above, a pyrylium salt of the formula:

ea e 3) A (III) err-R1 wherein a, R R R X, the position of the CHR R group and the position of the R group when halogen, are as previously defined, is reacted with a diamine of the formula:

H2N-( H) N112 wherein p and R are as previously defined. Typical diamines are ehylenediamine, propylenediamine, 1,2,- propylenediamine, hexamethylenediamine, dodecamethylenediamine, phenylenediamine, tolylenediamine, xylenediamine, etc.), in an inert organic solvent (e.g., benzene, toluene, etc.), in the molar proportions of about 2 moles of the compound of Formula III to each mole of the compound of Formula IV. Mixtures of two or more compounds coming under Formula III can be employed, if desired. Advantageously, the reaction mixture is heated for one or more hours, cooled and the crystalline product which forms is filtered otT, washed with a nonsolvent (e.g., absolute ethyl alcohol), and recrystallized from, for example, acetic acid and ethyl alcohol.

The compounds of Formula I in which Z and Z cornplete pyridinium nuclei are prepared as described for compounds of Formula II. Any compound of Formula I where R is alkylene is prepared to advantage by reacting one mole each of the appropriate heterocyclic bases having the formulas:

with one mole of a dihaloalkane having the formula: (VI) Halogen-R-halogen wherein R, R R Z, Z m and n are as defined previously.

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 form methylene bases with loss of positive charges on the nitrogen atoms, and also 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 alkali-release 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, providing a neutral or mildly alkaline hypo bath is used.

The formation of methylene bases is illustrated with the structure of Formula II above, wherein the groups R: CH

are ortho or para to the nitrogen atoms:

CH-R;

wherein d, p, 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 I 1,6-hexamethylene-bis(2-methyl-4,6-diphenylpyridinium iodide) c H C H 2-methyl-4,6-diphenylpyrylium iodide (2 moles, 7.4 g.) and hexamethylenediamine (1 mole, 1.16 g.) were suspended in benzene (50 ml.) and the mixture heated under reflux for one and one-half hours. The mixture was cooled and the solid product collected on a Buchner funnel, washed with absolute ethyl alcohol and dried. After one recrystallization from acetic acid and ethyl alcohol the yield of product was 2.72 g. (31%).

This compound under alkaline conditions forms a methylene base with loss of the positive charge on the nitrogen. This compound, at a ratio of 5 parts by weight to 1 part by weight of dye, mordanted the dye bis [3 methyl-l-p-sulfophenyl-2-pyrazolin-5-one-(4)]pentamethineoxonol, in gelatin, with no bleeding of the dye 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:

G. p-Methylaminophenol sulfate 4.5 Sodium sulfite, desiccated 90.0 Hydroquinone 8.0 Sodium carbonate, monohydrated 52.5 Potassium bromide 5.0

Water to make 1.0 liter.

The bleaching was increased when alkalinity of the developer was increased by the addition of sodium hydroxide. A sample was treated with a fixing bath of the following composition:

Sodium thiosulfate g 240.0 Sodium sulfite, desiccated g 15.0 Acetic acid, 28% cc 48 Boric acid, crystals g 7.5 Potassium alum g 15.0

C. was added 30 or 50 mgs. of mordant dissolved in 10 cc. of the appropriate solvent. The pH of the solution was adjusted to 4.55.0 with glacial acetic acid. To this was then added 10 mgs. of his [3-methyl-1-p-sulfophenyl- 5-pyrazolone-(4) pentamethine-oxonol dissolved in the appropriate 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 immersing a portion of the hand coating in stagnant, distilled water at 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 determined, 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.

In place of the 2-methyl-4,6-diphenylpyrylium iodide, there can be substituted in the above example an equivalent amount of any other of the intermediates coming under Formula III above, or any other of the diamines coming under Formula IV above to give the corresponding compounds which likewise function effectively as alkali-release mordants in photographic layers. For example, other suitable intermediates include 2-methyl-4,6- di-m-(and p)tolylpyrylium halides, 4-methoxy-2,6-dimethylpyrylium halides, 2,4,6-trimethylpyrylium perchlorate, 2,6-dimethyl-4-(3-pyridyl)pyrylium halides, and the like, which are reacted with a diamine such as 1,6-hexamethylene diamine, in accordance with the process of the above example.

The following example will serve to illustrate the preparation of a compound of Formula I in which the heterocyclammonium nuclei are not pyridinium nuclei.

EXAMPLE II 3,3-pentamethylene-bis (2-methylbenzothiazolium bromide) S C Ila-C accord- 1,12-dodecamethylene bis(n-2-isopropyl-4,6-di-ptolylpyridinium iodide) l, 4-tetramethylene-bis(n 4-methoxy-2,6-dimethylpyridinium bromide) 1,4-phenylene-bis n-2,4,6-trimethylpyridinium perchlorate) 1,4-tolylene-bis [n-2, 6-dimethyl-4- 3 -pyridyl) pyridinium iodide] 3,3-phenylene-bis(2-ethyl-4-phenylthiazolium iodide) 3,3-decamethylene bis (n-2-benZyl-4,6-di-p-tolylpyridinium iodide) 3,3-hexamethylene bis( l,Z-dimethylbenzimidazolium p-toluene sulfonate) 3,3-pentamethylene bis(2-methyl-4-phenylselenazolium chloride), etc.

These and other alkali release mordants are used to advantage to form non-diffusing salts with light-filtering acid dyes that are valuable for use in photographic elements.

The photographic elements prepared with the above described 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 emulsion layer. The mordant containing light-screening and antihalation layers are customarily prepared by coating on the support or photographic element 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 lightscreening 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 requirements 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 or carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in US. Patent 2,949,442, issued Aug. 16, 1960, polyvinyl alcohol, polyvinyl pyrrolidone, and others well known in the art. The abovementioned amphoteric copolymers are made by polymerizing the monomer having the formula:

wherein R represents an atom of hydrogen or a methyl group, and a salt of a compound having the general formula:

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 percent and preferably from 5-15 percent, 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, acryla-mide, methacrylamide, etc. Examples of these polymeric gelatin substitutes are copolymers of allylamine and and more particularly the dyes of the formula:

l I ia 5 Rs 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 carboxyalkyl 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 alkoxy 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. US. 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 hereocyclic 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, 2' represents the sulfa-substituted benzoxazole nucleus and when R represents a carboxyalkyl group or a sulfoalkyl group, Z' represents the non-metallic atoms necessary to complete a benzoxazole nucleus; Q represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the sulfophenyl pyrazolinone series and n is an inter 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(l car'boxymethyl 3- cyclohexylhexahydro-2,4,6-trioxo 5 pyrimidine) pentamethineoxonol, bis(1-butyl 3 carboxymethylhexahydro-2,4,6-trioxo 5 pyrimidine)trimethineoxonol, bis(1- carboxymethylhexahydro 3 octyl-2,4,6-trioXo--pyrimidine)methineoxonol, 4-[(3 ethyl-2-(3H)-benzoxazolylidine)-ethylidene]-3-methyl-1-(p-sulfophenyl) 2 pyrazolin-5-one monosulfonated, 4[4-(3-ethyl-2-(3H)-benzoxazolylidine) 2 butenylidene] 3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5-one monosulfonated, 4-[ 3 ,B-carboxyethyl 2(3H) benzoxazolylidene)ethylidene] 3- methyl-I-(p-sulfophenyl) 2 pyrazolin-S-one, 4- [4-(3-ficarboxyethyl 2(3H) benzoxazolylidene) 2 butenylidene] 3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5-one, bis(1-butyl-3-carboxyrnethyl 5 barbituric acid)trimethine oxonol, bis(1-butyl-3-carboxymethyl-S-barbituric acid) pentamethineoxonol, bis[3-methyl-l-(p-sulfophenyl) 2- pyrazolin-5-one-(4)]methineoxonol, bis[3-methyl 1 (psulfopenyl) 2 pyrazolin-5-one-(4)]trimethineoxonol, bis[3-methyl-1-(p-sulfophenyl)-2-pyrazolin 5 one-(4)] pentamethineoxonol, bis[3-methyl-l-(p-sulfophenyl) 5- pyrazolone-(4)]pentamethineoxonol, and 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-xsull:ophenyl )thiazolo 5,4-d] -thiazole disodium salt, 2,5 bis(o heXyloxy-x-sulfophenyl)thiazolo[5,4-d] thiazole disodium salt, 2,5-bis(o-hexyloxy-x-sulfophenyl) thiazolo[5,4-d]thiazole disodium salt, 2,5-bis(o-methylx-sulfophenyl)thiazolo[5,4-d]thiazole disodium salt, 2,5- bis(5-butyl 2 methyl-x-sulfophenyl)thiazolo[5,4-d]thiazole disodium salt, 2,5-bis(m-methyl-x-sulfophenyl)thiazolo[5,4-d]-thiazole disodium salt, 2,5-bis(p-propyl-xsulfophenyl)thiazolo[5,4-d]thiazole disodium salt, etc.; the ultraviolet absorbing dyes of Sawdey U.S. Patent 2,739,888, issued Mar. 27, 1956, such as 3-phenyl-2-phenylimino-S-o-sulfobenzal-4-thiazolidone sodium salt, 5-(4- methoxy-3-sulfobenzal)-3-phenyl-2-phenylimino 4 thiazolidone (sodium salt), 3-phenyl-2-phenylamino-5-[3-sul fobenzamido)-benzal] 4 thiazolidone (sodium salt), 3- benZyI-Z-phenylimino-5-o-sulfobenzal-4-thiazolidone (sodium salt), 5-(2,4-dicarboxymethoxybenzal)-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 halogen-substituted aliphatic acid such as mucobr'omic acid as described in White U.S. 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 naphthalene1,5-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-l,2-dione as described in Allen and Byers U.S. 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 U.S. Patent 2,726,162, issued Dec. 6, 1955; 1,3- dihydroxymethylbenzimidazo-2-one as described in July, Knott and Pollak, U.S. Patent 2,732,316, issued Jan. 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 23 carbon atoms, such as fl-methyl glautaraldehyde bissodium bisulfite as described in Allen and Burnes, Canadian Patent No. 588,451, issued Dec. 8, 1959; a bis-aziridine carboxamide such as trimethylene bis(laziridine carboxamide) as described in Allen and Webster U.S. Patent 2,950,197, issued Aug. 23, 1960; or 2,3- dihydroxydioxane as described in Jelfreys U.S. Patent 2,870,013, issued Jan. 20, 1959.

The photographic element utilizing our 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 lightsensitive 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 our invention:

FIG. 1 shows a light screening layer 10 comprising gelatin, an acid substituted filter dye and the mordant of the Example 1 coated over a light-sensitive silver halide 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 the 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 lightscreening layer 18 comprising gelatin, an acid substituted dye of the Example 1 coated over layer 19, and a bluesensitive silver halide emulsion layer 17 coated o-ver layer 18.

The use of our alkali-release mordants in lightscreening 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 transfer blanks of improved properties. The subject mordants are advantageously incorporated in photographic layers in a wide range of concentrations suitable to mordant acid dyes in the layer, such mordant concentrations being substantially higher than the amounts of addenda commonly used in photographic emulsion layers to achieve sensitizing elfects.

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 effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. An element comprising a support material having thereon a hydrophilic colloid layer containing at least one salt of a water-soluble acid dye and a mordant compound having the formula:

Bu l-o =o11-oH m 1=f-I-R-1 i =oH-oH).. 1=o- I E R7 X R; wherein m and it each represents an integer of from 1 to 2, R and R each represents a member selected from the class consisting of the hydrogen atom, a lower alkyl group, and an aryl group, R represents a member selected from the class consisting of a divalent alkylene group, a phenylene group, a tolylene group and a xylylene group, X rep resents an acid anion, and Z and Z each represents the nonmetallic atoms necessary to complete a nucleus containing a heterocyclic ring having 5 to 6 atoms in the said ring, said compound having a molecular Weight of at least 2. A light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially non-diifusible salt of a water-soluble acid dye with a compound of the wherein a. represents an integer of from 1 to 3, p represents an integer of from 1-18, R and R each represents a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group, with the --CHR R groups being substituted on a carbon atom, selected from the carbon atoms in the class consisting of the carbon atom in the 2 position and in the 4 position of the pyridinium ring, R represents a member selected from the class consisting of the hydrogen atom and a lower alkyl group, R represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkaryl group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, a 2-thienyl group, a 2-pyrryl group, a Z-indolyl group, a 3-indolyl group, a 2-furyl group, a 3-pyridyl group, and a 4-pyridyl group, such that when R, is a halogen atom, the halogen atom is substituted only on a carbon atom selected from the class consisting of a carbon atom in the 3 position and a carbon atom in the 5 position of the pyridiniu-rn ring, and X represents an acid anion, the said compound having a molecular weight of at least 300, said element containing light-sensitive silver halide.

3. A light-sensitive photographic element comprising a support material having thereon at least two hydrophilic colloid layers, at least one of said hydrophilic colloid layers being a light-sensitive silver halide emulsion layer and at least one of said hydrophilic layers containing at least one non-difiusible salt of a water-soluble acid dye with a compound of the formula:

GEE-31 wherein d represents an integer of from 1 to 3, p represents an integer of from 1-18, R, and R each represents a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group, with the CHR R groups being substituted on a carbon atom selected from the carbon atoms in the class consisting of the carbon atom in the 2 position and in the 4 position of the pyridinium ring, R represents a member selected from the class consisting of the hydrogen atom and a lower alkyl group, R represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkaryl group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, a halogen atom, a Z-thienyl group, a 2-pyr1yl group, a 2-indolyl group, a 3-indolyl group, a Z-furyl group, a 3-pyridyl group, and a 4-pyridyl group, such that when R, is a halogen atom, the halogen atom is substituted only on a carbon atom selected from the class consisting of a carbon atom in the 3 position and a carbon atom in the 5 position of the pyridinium ring, and X represents an acid anion, the said compound having a molecular weight of at least 300.

4. A light-sensitive photographic element comprising a support-material having coated thereon at least one light sensitive silver halide emulsion layer and having coated over said emulsion layer a hydrophilic colloid layer containing at least one substantially non-difiusible salt of a water-soluble acid dye with a mordant compound of the formula:

a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group, with the -CH R goups being substituted on a carbon atom, selected from the carbon atoms in the class: consisting of the carbon atom in the 2 position and in the 4 position of the pyridinium ring, R represents a member selected from the class consisting of the hydrogen atom and a lower alkyl group, R represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkaryl group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, a halogen atom, a 2-thienyl group, a Z-pyrryl group, a 2-indolyl group, a S-indolyl group, a Z-furyl group, a 3-pyridyl group, and a 4-pyridyl group, such that when R; is a halogen atom, the halogen atom is substituted only on a carbon atom selected from the class consisting of a carbon atom in the 3 position and a carbon atom in the 5 position of the pyridinium ring, and X represents an acid anion, the said compound having a molecular weight of at least 300.

5. A photographic element of claim. 2 wherein said hydrophilic colloid layer comprises gelatin.

6. A photographic element of claim 2 wherein said compound is 1,6-heXamethylene-bis(2-rnethyl-4,6-diphenylpyridinium iodide).

7. A photographic element of claim 2 wherein said compound is 1,6-hexamethylene-bis(2-methyl-4,6-diphenylpyridinium iodide) and the said hydrophilic colloid layer comprises gelatin.

8. A photographic element of claim 2 wherein said dye is bis[3-rnethyl-1wpsulfophenyI-Z-pyrazolin-5-one- (4)]-pentamethineoxonal and said compound is 1,6- hexamethylene bis(2 methyl 4,6 diphenylpyridinium iodide).

9. A light sensitive photographic element according to claim 2 wherein at least one of said dy'e components of said salts is a dye selected from the group consisting of 4 [(3 ethyl 2(3H) benzoxazolylidene)ethylideneJ- 3 methyl 1 p sulfophenyl 2 pyrazolin 5 one monosulfonated, bis(1 butyl 3 carboxy-methyl 5- barbituric acid)trimethineoxonol, 4-[4-(3-ethyl-2(3H)- benzoX-azolylidene) 2 butenylidene] 3 methyl 1- p sulfophenyl 2 pyrazolin 5 one monosulfonated, bis(1 butyl 3 carboxyrnethyl 5 barbituric acid) pentamethineoxonol, bis[3 methyl 1 (p sulfophenyl) 2 pyrazolin 5 one (4)]methineoxonol, bis[3- methyl 1 (p sulfophenyl) 2 pyrazolin 5 one- (4) ]trimethineoxonol and his [3-methyl-l-(p-sulfophenyl) 2 pyrazolin 5 one(4) ]pentamethineoxonol.

10. A light-sensitive photographic element according to claim 2 wherein at least one of said dye components of said salts is a dye selected from the group consisting of 4 [(3 ethyl 2(3H) benzoxazolylidene)ethylidene]- 3 methyl 1 p sulfophenyl 2 pyrazolin S one monosulfonated, bis(1 butyl 3 carboxy methyl 5- barbituric acid) trimethineoxonol, 4-[4-(3-ethyl-2(3H)- benzoxazolylidene) 2 butenylidene] 3 methyl 1 psulfophenyl 2 pyrazolin 5 one monosulfonated, bis[l butyl 3 carboxymethyl 5 b-arbituric acid) pentamethineoxonol, bis[3 methyl l (p sulfophenyl)- 2 pyrazolin 5 one (4)]methineoxonol, bis[3 methyl 1 (p sulfophenyl) 2 pyrazolin 5 one (4)] teimethineoroual and his [3-methyl-1-(psulfophenyl)-2- pyrazolin 5-one-(4)Jpentamethineoxonol, and the hydrophilic colloid comprises gelatin.

11. A photographic element comprising a support materral having thereon a hydrophilic colloid layer containmg at least one salt of a water-soluble acid dye and a mordant compound having the formula:

15 wherein m and n each represents an integer of from 1 to 2, R and R each represents a member selected from the class consisting of the hydrogen atom, a lower alkyl group, and an aryl group, R represents a member selected from the class consisting of a divalent alkylene group, a phenylene group, a tolylene group and a xylylene group, X reperesents an acid anion, and Z and Z each represents the nonmetallic atoms necessary to complete a 5 to 6 membered heterocyclic nucleus selected from the class consisting of a thiazole nucleus, at benzothiazole nucleus, 21 naphthiazole nucleus, a thianaphtheno-7',6',4,5-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, at naphthoselenazole nucleus, 2. thiazoline nucleus, :1 quinoline nucleus, an isoquinoline nucleus, 21 3,3-dialkylindolenine nucleus, at pyridine nucleus, an

References Cited UNITED STATES PATENTS 1/1962 Mader et a1. 9684 XR 9/1966 Whitmore 96-84 XR NORMAN G. TORCHIN, Primary Examiner.

R. H. SMITH, Assistant Examiner.

US. Cl. X.R. 9657; 117-33.3

US. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, 0.6. 20231 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,438,779 April 15, 1969 Donald W. Heseltine et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 13, line 39, "R," should read R Column 14 line 3 "goups" should read groups line 64 "teimethineoroual" should read trimethineoxonol Signed and sealed this 20th day of January 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr. E. SCHUYLER, J]

Attesting Officer Commissioner of Patents

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