US3726683A

US3726683A - Silver halide photographic light-sensitive element with dye layer

Info

Publication number: US3726683A
Application number: US00187553A
Authority: US
Inventors: N Yamamoto; M Yoneyama; H Ueda; Y Ono
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1970-10-07
Filing date: 1971-10-07
Publication date: 1973-04-10
Anticipated expiration: 1990-04-10
Also published as: JPS4916051B1; BE773459A; DE2150136B2; FR2111042A5; DE2150136A1; DE2150136C3; GB1339297A

Abstract

A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON AT LEAST ONE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AND AT LEAST ONE GELATIN LAYER CONTAINING (1) A POLYMERIC BASIC MORDANT HAVING MORE THAN 50% RECURRING UNITS SELECTED FROM THE GROUP CONSISTING OF 2-METHYL-1-VINYLIMIDAZOLE UNITS AND THE QUATERNARY SALTS THEREOF, 2- OR 4-VINYLPYRIDINE UNITS AND THE QUATERNARY SALTS THEREOF, ALKYLAMINOALKYLACRYLATE UNITS AND THE QUATERNARY SALTS THEREOF, AND ALKYLAMINOALKYLMETHACRYLATE UNITS AND THE QUATERNARY SALTS THEREOF, (2) AN OXONAL OR PYRAZOLONE-STYRYL TYPE DYE HAVING AN ACIDIC RADICAL IN ITS AROMATIC NUCLEUS, AND (3) A BETAINE-TYPE COMPOUND HAVING THE GENERAL FORMULA:

R1-N(+)(-R2)(-R3)-CH(-R4)-(CH(-R5))N-COO-

WHEREIN R1, R2 AND R3, WHICH MAY BE THE SAME OR DIFFERENT, EACH REPRESENTS AN ALIPHATIC HYDROCARBON RADICAL, R4 AND R5, WHICH MAY BE THE SAME OR DIFFERNT, EACH REPRESENTS A HYDROGEN ATOM OR AN ALIPHATIC HYDROCARBON RADICAL, AND THE TOTAL OF THE CARBON ATOMS IN R TO R5 IS FROM 8 TO 21, AND N IS 0 OR 1.

Description

United States Patent 3,726,683 SILVER HALIDE PHOTOGRAPHIC LIGHT-SENSI- TIVE ELEMENT WITH DYE LAYER Nobuo Yamamoto, Masakazu Yoneyama, Hiroso Ueda, and Yoshiaki Ono, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan No Drawing. Filed Oct. 7, 1971, Ser. No. 187,553 Claims priority, application Japan, Oct. 7, 1970, 45/88 132 Im. c1. Gti3c 1/84 US. CI. 96-84 A 6 Claims ABSTRACT OF THE DISCLOSURE A photographic element comprising a support having thereon at least one light-sensitive silver halide emulsion layer and at least one gelatin layer containing R. R;-+l}I-CH( JH ,.Coo

wherein R R and R which may be the same or different, each represents an aliphatic hydrocarbon radical, R and R which may be the same or different, each represents a hydrogen atom or an aliphatic hydrocarbon radical, and the total of the carbon atoms in R to R is from 8 to 21, and n is 0 or 1.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to a silver halide photographic light-sensitive element containing as its constituent photographic coatings composed mainly of a mordant, a dye and a betaine type surfactant which is employed as coating aids. The purposes of the present invention are to improve the wetting property of a photographic coating composition; to provide uniformity to a film after the application of the coating composition; and to present a silver halide photographic light-sensitive element in which the diffusion of the dye from the photographic coatings thus obtained to its adjacent photographic emulsion layer is prevented in the formation of the photographic coatings containing the dye which serves as light filtering layer such as yellow filter layer and light absorbing layer such as antihalation layer.

(2) Description of the prior art A photographic light-sensitive element is generally constituted of a support, such as one of cellulose triacetate, polycarbonates, polyesters, other synthetic polymers, glass or paper; a subbing layer, an antihalation layer, a photographic emulsion layer, an intermediate layer, a filter layer and a protecting layer etc., which are provided in order on the support. Thus, the photographic light-sensitive element is generally composed of a number of layers. These layers can not be applied uniformly where the coating composition is not employed along with a surfactant which serves to spread the coating composition uniformly and to improve its wetting characteristics. The surfactant also ice has the effect of suppressing the formation of foams and the repellency of the coating composition.

A coating composition containing a photographic emulsion having a different composition or a polymer material, such as gelatin, may be continuously coated in some cases in a multilayered manner on a support in the production of a color photographic light-sensitive element. In the case of further application of a coating composition or a photographic emulsion containing gelatin on a gelatin layer, more difiiculties are encountered in obtaining the required wetting characteristic in comparison with that encountered in the direct application of a gelatin coating composition to the support.

Saponin has been widely employed as coating aids for many years in the photographic industry and more widely utilized than a number of other surfactants. However, saponin has such disadvantages that it is liable to foam and there is large variation in its quality between batches due to the fact that it is natural product. For these reasons, a number of synthetic surfactants turn out to be employed in the photographic industry in recent years and a number of patents concerning this have been already published. The synthetic surfactants disclosed in these patents are not only employed as coating aids but also have the effects of static charge prevention, an increase in the solubility of color couplers, the permeability of a treating composition, a decrease in difiiculties due to a waterdrop, a disappearance of bubbles on the application of a gelatin sol to an emulsion layer which is set on cooling, development acceleration, and on prevention of stain due to the antihalation dye on a support. However, these effects show different characteristics in different types of the synthetic surfactants and in different compositions of photographic coating compositions, thus enabling in some cases a given photographic emulsion or gelling composition to obtain excellent results whereas in several cases of other compositions no improvement at all in its wetting and anti-repellent characteristics is observed. Accordingly,

it is proposed to apply a number of surfactants of different types to photography, since the synthetic surfactants are limited in use in many cases.

An example of the difficulties encountered in the coating process in the production of photographic light-sensitive element is to coat uniformly a mordant-dye type colloid dispersion in which the mordant and the dye are dispersed in a considerably diluted gelatin solution. Coating of this colloid dispersion has been usually employed as antihalation layer or filter layer in the photographic light-sensitive element. However, in this case, it was almost impossible to obtain a homogenous mordant-dye type dispersion and to apply it to a coating surface without foam formation or repellency.

Generally, in the case of application of a gelatin coating composition which comprises a basic mordant and an acidic dye, where a conventional anionic surfactant is being used as coating aids therefor, it is observed that not only is wettability of the coating composition unimproved but also undersirable difficulties may occur, i.e., cohesion of the mordant with the dye, and acceleration in the diffusion of the dye from the coated mordant-dye layer to its adjacent photographic emulsion layer to lower its sensitivity, etc. The diffusion of the dye is attributable to formation of a binding between the mordant and the anionic surfactant, which leads to isolation of the dye, due to the fact that the binding strength of the mordant and the anionic surfactant is stronger than that of the mordant and the dye. While, on employing non-ionic surfactants, such as saponin or polyalkylene-oxide derivatives, diffusion of the dye and cohesion of the mordant with the dye can be surpressed whereas wettability with a subbing layer is found to be bad, thereby causing repellency of a coating composition to occur. This phenomenon is especially remarkable under high speed coating operations. Cationic surfactants, such as N-alkyl-N,N-dimethyl-N- benzylammonium chloride, have similar antidiifusion effeet on the dye but striking cohesion of the dye and formation of fog, etc., are accompanied therewith, thus causing photogrpahic properties to be worse and hence there is little practical importance.

On the other hand, in order to solve these problems, some processes have been proposed, for example, such as that disclosed in the specification of British Pat. No. 1,124,490. In this patent, it is described that an N-alkylaminopropionic acid type amphoteric surfactant can be employed as coating aids for a coating composition forming a decolorizing filtering layer, comprising benzoxazolepyrazolonemelocyanine dye having a sulfonyl-, a sulfoalkylsulfophenyl-, a carboxylor a carboxylalkyl radical in its aromatic nucleus, and a basic high molecular weight mordant, such as a poly-alpha-methylalkyl-N-guanidylketoimine, to prevent diffusion of the dye and consequently to give a uniform mottleless film. However, satisfactory results were not always obtained as shown in the examples described hereinafter in such a case that a coating aid, such as sodium coco-beta-aminopropionate, described in the above British patent, is employed for a coating composition forming a decolorizating filtering layer, comprising a poly-Z-methyl-l-vinylimidazole type high molecular weight mordant and a dye, described, for example, in the specification of US. Pat. No. 3,445,231.

SUMMARY OF THE INVENTION The present invention relates to application of a gelatin solution containing a mordant and a dye, which is diflicult to coat.

The primary object of the present invention is to provide a photographic light-sensitive element having improved wetting and anti-repellent characteristics on the application of a gelatin solution comprising a basic high molecular weight mordant and an acidic dye, containing a betaine type surfactant, on a support or on other photographic layers.

Another object of the present invention is to apply a photographic composition without formation of any bubbles and other difiiculties on its application.

Another object of the present invention is to facilitate application where a photographic gelatin or emulsion layer is coated simultaneously or in order with another or still another gelatin or emulsion layer or layers.

Another object of the present invention is to prevent diffusion of the dye, thereby the sensitivity of this adjacent.

photographic emulsion layer is prevented from lowering.

Still another object of the present invention is to prevent cohesion of the mordant with the dye so as to give a stable coating composition.

It is found by the present inventors that these objects are attained successively by adding a betaine type surfactant having the general Formula I:

wherein R R and R which may be the same or different, each represents an aliphatic hydrocarbon radical, R and R which may be the same or different, each represents a hydrogen atom or an aliphatic hydrocarbon radical, and the total of the carbon atoms in R to R is from 8 to 21, and n is 0 to 1, to a gelatin composition containing a high molecular weight mordant having basic radicals, such as a polymer comprising more than 50% of Z-methyl-l-vinyl-imidazole units or the quaternary salts thereof, a polymer comprising more than 50% of 2-(or 4-) vinylpyridine units or the quaternary salts thereof, or a polymer comprising more than 50% of alkylaminoalkylacrylate units or alkylaminoalkylmethacrylate units or the quaternary salts thereof, and an acid dye, i.e., an oxanol or a pyrazolonestyryl type dye containing an acidic radical in its aromatic nucleus, such as a suite or a carboxyl radical, etc., the acid dye being fixed before developing treatment whereas decolorized during the course of the treatment.

These betaine compounds may be converted to its carboxylate in an aqueous alkali solution.

It was surprising that these betaine type surfactants which are employed in the present invention show peculiar effects in view of the same amphoteric type surfactant as described in the above British patent specification of No. 1,124,490. Accordingly, the betaine type surfactants represented by the above general formula are employed in the present invention to form a uniform film without having any undesirable properties, e.g., diffusion of the dye, cohesion (precipitation) of the mordant with the dye, and repellency etc. There is also no adverse influence on the photographic properties.

DETAILED DESCRIPTION OF THE INVENTION R to R in the above betaine type surfactant generally will contain an aliphatic chain of from 1 to 18 carbon atoms, for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, oleyl and the like.

The following mordants and dyes are illustrative of those which can be used in the present invention, but it should be understood that these compounds are not a limitation thereof, i.e., preferably employing any of an oxanol or pyrazolone-styryl type dye containing an acidic radical, such as a sulfo or a carboxyl radical, etc., and capable of being decolorized during the course of the treatment, or a basic high molecular weight mordant having a basic group in its main or branched chain, such as a poly-Z-methyl-l-vinylimidazole, a polyalkylaminoalkylacrylate or a polyalkylaminoalkylmethacrylate, or a poly- 2(or 4)-vinyl-pyridine group. Those who are skilled in the art can easily and clearly understand the dye groups having the specific chemical structure described by the terms of an oxanol or pyrazolone-styryl type dye, such as those dyes described in the specification of British Pats. Nos. 933,466, 906,083 and 1,034,044. Examples of such dyes are as follows:

Dye (3) Dye (3) Dye (6) The high molecular weight mordants which can be used in this invention generally have a polymerization degree of above about 50, although this is not a critical consideration. Examples of such mordants are given as follows:

Mordant 1 Mordant (2) Mordant (3) The betaine type surfactants which may be employed in the present invention are illustrated as follows:

Betaine compound (1) C Hz5- NC H: C O 0" Betaine compound 2) e 1o :1 IIICH;O O O- H:

Betaine compound (3) e" CsHu-+NCH2CH2C O O" Betaine compound (4) E C 4Hn+NC H: C O 0" Betaine compound (5) C uHzr-*NCH1 C O O Betaine compound (6) E CmHga+N-CHz C O O- Betaine compound (7) 5 C aHa1+NCH2 C 0 0 Betaine compound (8) These betaine compounds which are employed in the present invention can be easily synthesized by a method, such as that described in the Journal of the American Chemical Society, 69, 2095 (1947). For example, one mol of dodecylamine is dissolved in 300 ml. of ethyl alcohol, and 260 ml. of 85% formic acid is added dropwise thereto while maintaining the temperature at from 30 C. to 40 C. Thereafter, 210 ml. of 37% formaldehyde is added dropwise thereto at 40 C., after which the mixture thus obtained is refluxed until no further carbon dioxide is generated. After cooling, the reactant is neutralized 'with sodium hydroxide and separated into two layers. The upper layer is subjected to distillation to give N -dodecyl-N ,N-dimethylamine which is then reacted with an aqueous solution of sodium monochloroacetate at 90 C. for 3 to 4 hours under agitation to give the alphabetaine compound by a conventional method. This composition is purified by recrystallization from acetone.

This betaine compound may be employed alone as a coating aid, or may be employed together with a nonionic surfactant, such as saponin or a polyalkylene oxide derivative, or an amphoteric surfactant, such as alanine.

The betaine type compounds which are employed in the present invention are employed in a ratio of from 0.2 to 5% by weight based on the amount of gelatin in a photographic coating composition, capable of being'coated at a coating velocity of 100 meters/min. The proportion of mordant, dye and colloidal binder may be varied over a wide range and will depend on the specific requirements of the photographic element being produced.

It should be appreciated that the present invention is applicable to a photographic light-sensitive element con taining at least one layer selected from a decolorizing antihalation layer, a filter layer and intermediate layers, composed of the mordant, the dye and the betaine type surfactant. These layers are especially necessary to obtain a color photographic light-sensitive element having high resolving power and sharpness, serving as an effective antihalation layer when the base is not colorized, affecting little irradiation between the layers and capable of being applied to an emulsion layer on a support. These layers are also effective to control spectral sensitivity of the emulsion layer on which the layers are coated, thereby improving the properties of the color photographic lightsensitive element. The following examples are presented to illustrate the present invention.

EXAMPLE 1 -5 ml. of a 4% aqueous solution of saponin is added as a coating aid to one kg. of a silver halide iodobromide emulsion containing a color coupler to give a photographic emulsion which is then applied to a cellulose triacetate support subjected to subbing so as to be 3 microns in thickness in the dried condition. Independently, a solution containing 50 parts by weight of gelatin, 6 parts by weight of Dye (1) and 5 parts by weight of Mordant (l), is diluted with water so that 1.6% by weight of gelatin is contained in the diluted solution. To the solution thus obtained are added as coating aids Betaine Compounds (1), (4) and Coating Aids (1) to (7) for comparison, separately, to give coating compositions in which 2.5% or 7.5% by weight of each of the compounds is contained based on the amount of the gelatin. These coating compositions are then applied to the photographic emulsion 8 layer. The degree of repellency and the wetting characteristics in this case are shown in Table 1.

TABLE 1 Amount added (percent) Number of Wetting gelatin repelleney width Coating aid added weight per 10 m? (percent) Bet-nine compound:

5 0 100 5 0 100 Coating aid 1 (for comparison):

2. 5 70 22 1g ;2 6 0 (2) g 30 go 55 5 (3) g 33 95 5 80 a 2" 0 0 (5) g 12 95 25 5.2 g 5 0 (7) 7. s 12 No'rn.'l.he number of repellency represents number of repellency per m3 of coated area. The wetting width represents the relative value of the wetting width. When a. photographic support is wet-ted fully over its width, the wetting width is designated as 100.

1 See the Dllowing table:

Coating aids C 2508 OsNa R represents a hydrocarbon radical obtained from coco-oil.

From the results shown in Table 1, it is observed that the wetting characteristics are markedly improved and there exists a large number of repellencies even in the case that the amount of each of compounds 1) to (7) for comparison is increased to 7.5% byweight based on the amount of the gelatin. Especially in the case of compound (4) for'comparison, cohesion of the mordant with the dye'occurred to form a yellow lumpy material. Also, in the case of compound (1) for comparison, it is observed that recirculation is formed on the surface of the coatings. Contrary to this, no repcllencies are observed and uniform films can be formed even in the case in which 2.5% by weight of betaine compounds (1), (4) are employed separately, based on the amount of the gelatin. There is also no undesirable influence on the photographic characteristics.

EXAMPLE 2 In the same manner as described in Example 1, a silver halide photographic emulsion containing a color coupler is applied to a cellulose triacetatc support subjected to subbing so as to be 3 microns inthickness in the dried condition. Independently, solutions containing 50 parts by weight of gelatin, 2.5 parts by'weight of a mordant and 5 parts by weight of each of Dyes (2) to (6) are diluted separately with water so that 1.6% by weight of gelatin is contained in each of the diluted solutions. To each of these solutions are added separately Betaine compound (1) as coating assistant so as to be 2.5% by weight based on the amount of the gelatin to give coating compositions. These coating compositions are applied to the silver halide photographic emulsion. In this case, no repellency is ob served and uniform films are obtained with all of the samples. Accordingly, this fact means that the Betaine compounds in the present invention show excellent coating characteristics, essentially regardless of the dyes, i.e., x0- 1101 type dyes having a sulfonyl or a carboxyl radical and pyrazol type dyes.

EXAMPLE 3 A silver halide photographic emulsion containing a color coupler is applied to a cellulose triacetate support, subjected to subbing so as to be 3 microns in thickness in the dried condition. Independently, solutions containing 50 parts by weight of gelatin, 6 parts by weight of Dye (1) and parts by weight of each of Mordants (1) to (5) are diluted separately with water so that 1.6% by weight of gelatin is contained in each of the diluted solutions. To each of these solutions are added separately Betaine compound (4) as coating aids so as to be 2.5% by weight based on the amount of the gelatin to give coating compositions which are then applied to the silver halide photographic emulsion layer. Also in this case, no repellency is observed and an excellent coated surface is obtained in all of the samples, regardless of the dyes.

EXAMPLE 4 The applicability of the Betaine compound as coating aidsto anti-halation composition to which Dye (1), Dye (4) and Dye (6) are added is examined. A solution containing 50 parts by weight of gelatin 2, parts by weight of Dye (l), 2 parts by weight of Dye (4), 2 parts by weight of Dye (6) and 5 parts by weight of Mordant (2) is diluted 'with water so that 1.6% by weight of gelatin is contained in the diluted solution. To this solution is added Betaine compound 1) as coating aids so as to be 2.5% by weight based on the amount of the gelatin, after which the mixture thus obtained is supplied to a support subjected to subbing. Consequently, no repellency is observed and an excellent film is obtained.

EXAMPLE 5 Preparation of a red-sensitive emulsion To a silver iodobromide photographic emulsion which is prepared by a conventional method is added a methanol solution containing 0.2 millimol of anhydro-5-, 5'-dichloro-3', 9-diethyl-3-(8-sulfobutyl)-selenacarbocyaninehydoxide per one millimol of the silver halide. Independently, one gram of N-n-dodecyl-l-hydroxy-4-chloro-2- naphthoamide is dissolved as a cyan coupler in 2.0 ml. of dibutylphthalate under heating, after which the solution thus obtained is poured into 10 grams of the aqueous solution containing 10% by Weight of gelatin to give an emulsified dispersion, sodium dodecylsulfate being employed as a dispersing agent therefor. This emulsified dispersion is then added to the silver halide emulsion containing the photo-sensitive coloring matter so that 0.15 gram of the coupler is contained per one mol of the silver halide. Further, to the mixture thus obtained are also added S-methyl- 7-hydroxy-1,3,5-triazaindoridine as a stabilizer, 2,4-dichloro-6-hydroxy-1,3,5-triazine as a hardening agent, Betaine compound (1) as a coating aid, the amount of which being 2.0% by weight based on the amount of the gelatin, citric acid as a pH-adjusting agent and partially saponified polyvinyl alcohol as an anti-turbidity agent (British Pat. No. 1,226,158) to give the red-sensitive emulsion.

Preparation of a green-sensitive emulsion To the silver iodobromide photographic emulsion is added 0.2 millimol of 3,3,9-triethyl-5,5-diphenyl-oxocarbocyanineiodide per one mol thereof. Independently, one gram of 1-phenyl-3-dodecylamino-5-pyrazolone is dissolved as a magenta coupler in 2 ml. of tricresylphosphate under heating, after which the solution thus obtained is poured into 10 grams of the aqueous solution containing 10% by weight of gelatin to give anemulsified dispersion, sodium dodecyl sulfate being employed as a dispersing agent therefor. This emulsified dispersion is then added to the silver halide emulsion containing the photosensitive coloring matter so that 0.15 gram of the coupler is contained per one mol of the silver halide. To the emulsion thus prepared are also added the stabilizer, the hardening agent, the coating assistant, the pH adjusting agent and the ant-turbidity agent, which are the same as described in the preparation of the red-sensitive emulsion to give a green-sensitive emulsion.

Preparation of a blue-sensitive emulsion To the silver iodobromide photographic emulsion is added an emulsified dispersion prepared by dissolving as a yellow coupler one gram of 4-dodecylbenzoyl-2- methoxyacetoanilide in 2.5 ml. of dibutylphthalate under heating and pouring the solution thus obtained into 10 grams of the aqueous solution containing 10% by weight of gelatin, sodium dodecylbenzenesulfonate being employed as a dispersing agent therefor, so that 0.22 gram of the coupler is contained per one mol of the silver halide. Further to the emulsion thus prepared are also added the stabilizer, the hardening agent, the coating aid, the pH-adjusting agent and the anti-turbidity agent, which are the same as described in the preparation of the red-sensitive emulsion to give the blue-sensitive emulsion.

Preparation of a coating composition for an intermediate layer A solution containing 50 parts by weight of gelatin, 3 parts by weight of Dye (5) and 5 parts by weight of Mordant (2) is diluted with water so that 1.6% by weight of gelatin is contained in the diluted solution. To the solution thus obtained is added as a coating aid Betaine compound (1) so as to be 2.5% by weight based on the amount of the gelatin, after which a hardening agent is further added thereto to give the coating composition for the intermediate layer.

Preparation of a coating composition for a yellow filter A solution containing 50 parts by weight of gelatin, 5 parts by weight of Dye (1) and 5 part by weight of Mordant (2) is diluted with water so that 1.6% by Weight of gelatin is contained in the diluted solution. To this so lution is added Betaine compound (4) as a coating aid so as to be 2.5% by weight based on the amount of the gelatin to give the coating composition for the yellow filter.

Production of a silver halide color photographic light-sensitive element The photographic coating compositions thus prepared are applied successively in layers to a cellulose triacetate support as the anti-halation layer (Example 4), red-sensitive emulsion layer, intermediate layer, green-sensitive emulsion layer, yellow filter layer, blue-sensitive emulsion layer and protecting gelatin layer separately.

Exposure and developing treatments The color photographic light-sensitive element is sub jected to an exposure treatment for a period of & second by the use of NSG-III type sensitometer having a light source of 4,800 K. The color photographic lightsensitive element thus treated is then subjected to developing treatment by the use of a developer having the following composition for a period of 10 minutes at 24 C. followed by washing with water, hardening, washing with water and reversal exposure treatment.

Developer composition: G. N-methyl-p-aminophenol 4.5 Hydroquinone 4.5 Anhydrous sodium sulfite 50 Sodium carbonate 30 Potassium bromide 1 Potassium thiocyanate 2 Water to make 1 liter.

Thereafter, the color photographic light-sensitive element thus treated is subjected to color developing treatment for a period of 15 minutes at 24 C. by the use of a color developer having the following composition followed by wasing with water, bleaching, washing with water, fixation and washing with water to give a transparent color positive image.

Color developer composition:

Benzyl alcohol ml 6 Anhydrous sodium sulfite g 4 Sodium phosphate g 40 Potassium bromide g 0.5 Sodium hydroxide g 1.5 Ethylenediamine ml 5 Cytradinic acid gl p Amino N ethyl-N-beta-methane-sulioneamide-ethyl-m-toluidine sulfate g 11 Water to make 1 liter.

The positive image thus developed on the cyan, magenta and yellow layers shows no color turbidity due to poor silver removal and stains, etc., to give a sharp color photograph having no undesirable effects on its other photographic characteristics.

EXAMPLE 6 This example illustrates that the betaine compound is rather employed to improve the mordanting eificiency of the mordant and not decrease it.

A solution containing 50 parts by weight of gelatin, 6 parts by weight of Dye (2) and 5 parts by weight of Mordant (2) is diluted with water so that 1.6% by Weight of gelatin is contained in the diluted solution. To this solution are added Betaine compounds (1), (2), (4), and Coating aids (1.), (2), (7) for comparison, separately, so as to be 3.0% by weight based on the amount of the gelatin, further a hardening agent being added thereto to give a coating composition. Each of these coating compositions is then applied to a cellulose triacetate support on which anti-halation and gelatin layers comprising colloidal silver are previously coated, so as to provide a 2 microns dry thickness, and dried. A blue-sensitive emulsion layer containing a yellow coupler prepared by the same method as described in Example 5 is further applied thereto so as to be 5 microns in thickness in the dried condition followed by drying. Independently, the blue-sensitive emulsion layer is applied to the support and dried to give samples without applying a yellow filter layer thereto. Each of the samples thus prepared is then subjected to exposure and developing treatments similar to that described in Example 5 to give a yellow positive image. A relative value of the degree of exposure to 1.0 of the concentration of the yellow positive image is determined as the relative speed, and results to 100 of the relative speed of coating aids (2) and number of repellencies are shown in Table 2.

From the results shown in Table 2, it is observed that the lowering in the sensitivity is very large when Coating aids (l), (2) and (7) are employed, separately. This may be due to the diffusion of the dye in the yellow filter layer to the blue-sensitive emulsion layer provided thereon.

Moreover, the sensitivity of the blue-sensitive emulsion layer is found essentially to not be lowered when Coating aid (2) is employed, but repellency occurs in a large amount and an excellent film is not obtained. On the contrary, lowering in the sensitivity is hardly observed when Betaine compounds (1), (2) and (4) are employed, separately, as understood in comparison with the sensitivity of blue-sensitive emulsion layer having no yellow filter layer, and also no repellency is observed to give an excellent film.

What is claimed is:

1. A photographic element comprising a support having thereon at least one light-sensitive silver halide emulsion layer and at least one gelatin layer containing (1) a polymeric basic mordant having more than 50% recurring units selected from the group consisting of Z-methyl-l-vinylimidazole units and the quaternary salts thereof, 2- or 4-vinylpyridine units and the quaternary salts thereof, alkylaminoalkylacrylate units and the quaternary salts thereof, and alkylaminoalkylmethacrylate units and the quaternary salts thereof,

(2) an oxonal or pyrazolone-styryl type dye having an acidic radical in its aromatic nucleus, and

(3) a betaine-type compounds having the general formula:

wherein R R and R which may be the same or different, each represents an aliphatic hydrocarbon radical, R and R which may be the same or dilferent, each represents a hydrogen atom or an aliphatic hydrocarbon radical, and the total of the carbon atoms in R and R is from 8 to 21, and n 0 or 1. 2. The photographic element according to claim wherein said gelatin layer is a light filtering layer.

3. The photographic element according to claim wherein said gelatin layer is a light absorbing layer.

4. The photographic element according to claim wherein said betaine-type compound is 5. The photographic element according to claim wherein said betaine-type compound is 13 14 6. The photogrphic element according to claim 1, 3,434,841 3/1969 Kuhrt 96114.5 wherein betaine-type compound is 3,445,231 5/ 1969 Nishio et a1 9684 A FOREIGN PATENTS u 5 680,964 2/1964 Canada 961145 H; References Cited RONALD H. SMITH, Pnmary Exammer UNITED STATES PATENTS US. Cl. X.R. 2,197,809 4/1940 McQueen 96114.5 10 3,408,193 10/1968 Wolf et a1. 96-84 R