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Publication numberUS2698794 A
Publication typeGrant
Publication dateJan 4, 1955
Filing dateApr 15, 1950
Priority dateApr 15, 1950
Publication numberUS 2698794 A, US 2698794A, US-A-2698794, US2698794 A, US2698794A
InventorsLeopold Godowsky
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Mixed packet photographic emulsions
US 2698794 A
Images(1)
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Description  (OCR text may contain errors)

United States Patent "ic 298,794

Patented Jan. 4, 1955 colloid carrier. The couplers are incorporated in the emulsion by dissolving them in a substantially water- 2,698,794 insoluble slolvent fgr tars coupler, and tilispersinlg thistlfllt1 n in e atin n in it to atino-siver MIXED PACKET PHOTOGRAPHIC EMULSIONS 5 3, 5, a a g a ge a 1 e The silver halide used in these emulsions may be optically sensitized, and ordinarily two or more emulsions sensitive to diiferent regions of the visible spectrum will be employed.

Application April 1950 Serial 156 066 10 The following couplers are suitable for use according to my invention:

11 Claims. l- CYAN COUPLERS This invention relates to color photography and par- 15 ticularly to mixed packet photographic emulsions. Cl- -NHO O-CHz-O-QOsHn There have been many prior suggestions of mixed grain photographic emulsions, that is, photographic systems $511 in which differently sensitized silver halide grains are incorporated in a single photographic emulsion layer and i used to produce ditferently colored photographic images in the layer. Mixed grain systems have a number of ady p ly 0 0-5- vantages, chief among which is the simplicity of coating methylphenol a single emulsion layer rather than several layers. Other 0H advantages are the improved definition obtained by having the differently sensitized particles juxtaposed in a 01- NHC mam-000,11

single layer, and the simplification of processing which E is generally obtained. CH? 5 6 Prior mixed grain photographic methods have not been successful either because it was impossible to secure color separation with them, that is, effectively to prevent color formation around unexposed silver halide grains, or be- 2-[a-(2,4'-tert -amylphenoxy)-n-butyrylamino]4,6-

cause the colored particles formed in the process were -7 too grainy. OH

It is therefore an object of the present invention to provide a method and sensitive material for mixed packet O color photography according to which difficulties in the I prior art are overcome and a practical result is achieved. CH 02115 By mixed packet I mean a process or an emulsion in 3 which differently color-sensitive silver halide grains hav- 9 a ing color-formers associated therewith are incorporated in 1 a single Photographic layer for the P p of producing 2-[a-(4-tert.-amylphenoxy)-n-butyrylamino1-4-chlor0- differently colored photographic images in that layer by 5-methy 'D a single exposure. on

Thefse objects are acgomplished by first gislpgrsing 1a I colororming compoun in a peptize si ver a i e emu sion, preferably a gelatino-silver halide emulsion. The CONH (CH2)! 0 emulsion may contain the normal amount of gelatin, or a 1 lower amount than usual may be present. For example,

the gelatin content may be from 4 to 200 grams or more Leopold Godowsky, Westport, Conn., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey per 100 grams of silver halide. The emulsion containing the coupler dispersion is then mixed with a suitable naphthamlde water-dispersible polymer which does not react with gela- OH tin, and to the mixture there is added a solution of a I polymeric packet-forming component. Two or more of CONH(CH2)4O 05H the resulting packet dispersions which contain silver halide sensitized to different spectral regions, are then mixed with additional gelatin or another water-soluble polymer 05H to form the mixed packet emulsion, preferably by adding G1 the gelatin or polymer to each packet dispersion separately before mixing them. 1-hydroxy-4-chloro-2-[6-(2',4'-di-tert.-amy1phenoxy)-n-buty1]- The accompanying drawing is a flow sheet illustrating aphthamlde the 1Vslteps 1n rrtry process. th f 1 h rd 1 MAGENTA COUPLERS y mven 1cn invo ves e use 0 a s1 ver a1 e emu sion containing a non-diffusing color-forming compound NE 000mm or coupler which is reactive with the oxidation product 0 of a primary aromatic amino developing agent to form a dye image. These couplers are preferably incorporated in the emulsion as described in Jelley and Vittum U. S. Patent 2,322,027, but may be directly dispersed in the 1-pheny1-3-palmltoylamino-5-pyrazolone N=C-NHOOC 1 0 Cs n (Iii-CH2 0 1- [p- (p'-tert.-butylphenoxy) -phenyl -3- [mp-tert-amylphenoxy) benzoylamino -5-pyrazolone 1-( p- [p-tert.-butylphenoxy]-phenyl)-3- (m-[p-toluenesulfonylamino]-benzoylamino-o-pyrazolone) YELLOW COUPLERS N-(p-benzoylacetuminobenzenesulphonyl)-N-(n-amy1- p-tert.-amy1am'1ine 6-0 euro onnQ-sm-st-mmn-G N- p-benzoylacetnminobenzenesulphonyl -N- ('y-phenylpropyl) -aniline O4: 0 onto ONHQSOz-T-OOHQ N- p-benzoylacetaminobenzenesulphonyl) -N-benzyl-p-to1uidine O0 0 orno ONHO-Sm-n- CHmO N-(p-benzoylacetaminobenzenesulphonyl) -N-('y-pl1euyl propyl) ptert.-amy1anili11e -o 0 01120 ONHO-SOHTT-(CHQs-O N- (p-benzoylacetaminobenzenesulphonyl -N- ('y-phenylpropyl)-(o)-, (m), or (p)-toluidine After making the dispersion of coupler in gelatinosilver halide emulsion, the dispersion is added to a water solution of a water-soluble polymer or water-soluble salt of a polymeric material containing salt-forming acid groups, such as the copolymer of methacrylic acid and methyl-tt-methacrylate (Minsk, Weyerts and McDowell U. S. Patent 2,391,181) algin (alkali metal salt of polymeric d-mannuronic acid), carboxy methyl cellulose (Collins, Freeman and Anthonisen U. S. Patent 2,278,612), and cellulose sulfate (Belgian Patent 448,249). The Water-soluble polymer is mixed with the gelatin of the dispersion and acts as a modifying agent, so that small packets, each containing appropriately sensitized silver halide and color-forming coupler, can be formed.

To the mixture of dispersion and water-soluble polymer or salt, mentioned above, .there isthen added, preferably with stirring, an aqueous solution of a polymeric packet-forming component or gelatin reactant, or vice versa. The polymeric, packet-forming component consists of a polymeric carbon chain having recurring phenyl groups and carboxyl groups, and preferably also carboxylic acid amide groups or imide groups or both and is used as the water-soluble salt, such as the ammonium, sodium, potassium or lithium salt. The polymeric packet-forming component is preferably an inter-polymer of styrene and an o B-UHSHUIl'fiEEd carboxylic acid, part of whose carboxyl groups may have been converted to amide or imide derivatives or both, such as interpolymers of styrene-maleic acid, styrene-acrylic acid, styrenemethacrylic acid or styrene-itaeonic acid.

The mixture of coupler-silver halide dispersion, watersoluble polymer and polymeric packet-forming component now consists of particles or packets of gelatin, associate with polymeric packet-forming component, containing silver halide and coupler, the packets being dispersed in an aqueous medium containing additional gelatin or another film-forming water-soluble polymer. This is finally mixed with at least one other similarly made packet dispersion containing differently-sensitized silver halide and a different coupler to form the finished mixed grain emulsion. The finished emulsion is then ready for coating on a suitable support, such as glass, cellulose ester, or paper.

In the preparation of the system described above, that is, gelatin, water-soluble polymer, and packet-forming component, the ingredients must be present in a fairly QCfillltr') ratio. If the gelatin is present in approximately 0.7% aqueous solution (an appropriate concentration for making an emulsion), then the Water-soluble polymer should be present in an amount from about 1 to 2 times that of the gelatin, and the packet-forming component should be present in an amount from 0.01 to 0.5 times that of the gelatin. Within these ranges the three-component systems exhibit a definite degree of optical turbidity. If this turbidity is measured in optical density per cm. of mixture at 30 C., using orange-colored light, of about 5800 A. U., the optical density is greater 0.05, and is generally of the order of 0.1.

Suitable polymers of styrene with maleic acid or its derivatives are represented by the following formula:

I solo 0 its 2/ Suitable polymers of styrene with acrylic acid or its derivatives may be represented by the following formula:

R R R R R CHrCH-CHr-QFCHz--CHz--Cflr-CHr- 0 CO CO (30 l Y OH Z In each formula H NH2 NHR' NRTz R=hydrogen CH3 CzHs R=alkyl of less than six carbon atoms or aryl Z=NH NR OH groups on each carbon atom to which Z is attached.

n=the number of units in the polymer chain.

It will be understood that the above structural formulas are illustrative only, and are not limiting as to ratios and unit arrangements of constituents.

The polymeric packet-forming components of the first structural formula above may be prepared by forming an interpolymer of styrene and maleic anhydride, and then treating the polymer with ammonia, a primary or secondary amine, or water, as indicated by the following formula using ammonia:

Formation of these polymers is described in Condo, Krister and Lundquist U. S. Patent 2,286,062 and McDowell and Kenyon U. S. Patent 2,313,565.

Interpolymers of styrene and acrylic anhydride or a-methacrylic anhydride may be used instead of the interpolymer of styrene and maleic anhydride, as indicated by the following formula using ammonia:

Imide groups along the polymer chain may result from the interaction of adjacent amide groups or an amide and a carboxyl group.

These polymers may also be prepared by direct polymerization, e. g., styrene, acrylamide or N-substituted acrylamide, acrylic acid; or styrene, maleamic acid or N-substituted maleamic acid.

In order to ascertain'the packet-forming components which are suitable for use in my process, the following test may be made:

A solution or dispersion of the polymeric compound to be tested, gelatin, and the sodium salt of methylmethacrylate-methacrylic acid polymer is made up in water so that the final concentrations are gelatin, 0.7%; methylmethacrylate-methacrylic acid salt, 1.67 times the amount of gelatin; and polymeric compound, 0.1 to 0.5 times the amount of gelatin. The gelatin is a deashed calfskin gelatin having an isoelectric point of approximately 4.8. The polymeric compound is added as an approximately 2% solution in ammonium hydroxide of pH 7.5. When vigorously stirred, this mixture is characterized by its ability to scatter or diffuse light transmitted through it. With polymeric compounds suitable for my process, the mixture must exhibit an optical density of at least 0.05 per centimeter of mixture, when measured at 30 C. wlth orange-colored light of approximately 5800 Angstrom units wave length.

The packet-forming components were prepared as follows:

Example 1.Styrene-maleic anhydride interpolymer Into a 12-liter all glass reflux outfit equipped for an hydrous conditions the following were measured:

234 gm. distilled styrene 220.5 gm. maleic anhydride 3188 ml. dry benzene 4.25 gm. benzoyl peroxide Example 2.-P0lystyrene-maleamic acid polymer 50 gm. of polystyrenemaleic anhydride were added gradually to 250 ml. of 28% ammonium hydroxide 111 a 500 ml. Erlenmeyer flask with stirring from a mixer to form a slurry. After stirring for eighteen hours at room temperature a viscous, clear colorless dope was obtained. 300 gm. of this dope was diluted to approximately 2% solids with water and 48% hydrobromic acid was added to it until it was -just acid to Congo red. The solid that was formed was separated by filtration, and leached with absolute alcohol until the wash solutions were bromide free. The solids were put to dry in an oven at 60 C.

20 gm. of the solid were doped to form a 5% dope by weight in water made alkaline with 13 ml. of 20% sodium hydroxide. pH=8.63.

Example3.Polystyrene-maleamic acid ammonium salt The following reagents were put to reflux in an all glass reflux outfit equipped with a mechanical stirrer. Conditions were maintained anhydrous by calcium chloride tubes on all openings to the atmosphere.

49 gm. maleic anhydride (Eastman white label) 52 gm. distilled styrene 1500 ml. dry toluene 2.0 gm. benzoyl peroxide The reaction mixture was heated for 2% hours on a steam bath without stirring and then allowed to cool to room temperature. A small sample of the solids was withdrawn, washed with fresh benzene, and put to dry for analysis and viscosity purposes.

The stirrer was turned on and dry ammonia was bubbled into the reaction mixture continuously for 3 /2 hours. During this time the temperature within the reaction mixture rose from a starting temperature of 23 C. to 45 C. and then returned to 23 C. The solids were filtered off on a Biichner funnel, washed with toluene, and put to dry in a vacuum oven at 60 C. over night.

The residual toluene was then extracted with absolute alcohol by stirring the product with 23 1. portions of absolute ethyl alcohol and filtering onto a Biichner funnel. The product was then dried as above.

Forty grams of the polymer were gradually added to 200 ml. of water in an Erlenmeyer flask with mechanical stirring. The solution was kept slightly alkaline by the portion-wise addition of 28% NH4OH. The pH was never allowed to exceed eight. A clear colorless dope was obtained which was then adjusted to 15% solids by weight by the addition of distilled water. The pH of this solution was 6.38.

Example 4.-Amm0nium salt of stryene-maleic acid interpolymer 10 gm. of a styrene-maleic anhydride interpolymer were heated with 200 ml. of distilled water on a steam bath for 6 hours and then left at room temperature for 65 hours. After this period of hydrolysis, 28% NH4OH was added to the mixture portion-wise while it was mechanically stirred, using no more ammonium hydroxide than was necessary to effect solution. The solution was then diluted to 400 g. total weight with distilled water. The pH of the solution was 6.34.

Example.5.Sodium salt of styrene-maleic acid interpolymer The procedure was similar to the above example except that 10% sodium hydroxide was used to effect solution of the hydrolyzed styrene-maleic anhydride interpolymer. The pH of the final solution was 8.16.

Example 6.Styrene-acrylic anhydride copolymer The following were heated in an all glass reflux outfit on a steam bath under anhydrous conditions for 24 hours:

42 gm. distilled acrylic anhydride 35 gm. distilled styrene 500 ml. dry 1,4-dioxane 0.8 ml. 30% H202 The reaction mixture was shaken frequently. During the first hour the mixture began to become cloudy; shortly after this period, the mixture became very cloudy and set to a gel. After cooling to room temperature, the solids were broken up, separated by filtration and washed with dry dioxane. The polymer was dried in vacuum desiccator under constant water pump vacuum, with a calcium chloride tube in the vacuum line.

Preparation of the styrene-acrylic acid-acrylamide polymer was carried out similar to the preparation of the polystyrenemaleamic acid polymer in aqueous ammonium hydroxide, only using the above intermediate. Example 7.Il/IethacryZic anhydride-styrene interpolymer 61.6 gm. distilled rnethacrylic anhydride 41.6 gm. distilled styrene 1.0'nil. 30% H202 600ml. dry 1,4 dioxane The solution gelled after the first hour and half of heating. When the reaction mixture had cooled to room temperature after the 16 hour heating period, the gel was manually broken up and washed with dry 1,4-dioxane in a Biichner fur product was dried.

The preparation or": the styrene methacrylic acid, methacrylamide polymer as carried out exactly similar to the preparation oi the polystyrene-malearnic acid polymer in ammonium hydroxide.

Example 8.-lvla1cic anhydride: styrene: vinyl acetate imerpolymer The following were ut in a resin reaction flask equipped with a reflux condenser and mechanical stirrer:

.-[Malermzic acidnszyreiiemfizyl acetate ifllifpolymer Exalizpie 9 Fifty grains of the styrenewinyl acetatc-malec anhy dride interpolymer (Example 8) w .e "(l(i'l o 28 per cent ammonium hydroxide i mixture was stirred for id hours, during which time solution occurred a viscous dope was obtained This was dil ted to 1220 g .335 with distilled water, 1 ng a 5 per cent solution. Two hundred ms of the above dope were diluted to 750 cc. with dist led water and t1 -n made acid to Congo red with hydrobromic d. The precipitate was filtered and "then extracted with absolute ethyl alcohol until bromide-free. The product was then dried in vacuum. The yield was 7 grams. This was dispersed by stirring in water containing ammonium hydroxide.

Example Iri a Jaime aizliytiride:styreire:bmy! acryl'ate interpoz'yliter The following were put in an all-glass reflux outfit equipped for anhydrous conditions on a steam bath to reflux for 2 hours:

36.4 grams distilled styrene 49.0' grams maleic anhydride 19.2 grams distilled butyl acrylatc 1.0 gram benzoyl peroxide 750 ml. dry benzene When the reaction was completed. t I ture was cooled to room temperature. The result! cipitate was isolated by filtration on :r B ichner washed with dry benzene, and put to dry i desiccator under couS*' t water pump vac The yield was 76.6 grams. inherent visco y, t r (See Cragg, J. ColloidScience, vol. 1, page 261, 31946, for description of inherent viscosity.)

Example 11.Ma!eamic aciekbutyl acrylazeuryrcne interpolymer Forty grams of the interpolymer of styrene-butyl acrylate and maleic anhydride intcrpolyrner (Example 10) were added with stirring to 269 c. of 28 per cent ammonium hydroxide kept chilled in an ice bath. In minutes a viscous dope was obtained and 100 cc. of water by filtration and washed with water 1 nil bi wereadded. The reaction mixture was stirred for 2. hours with continued chilling. diluted. to 1600 grams and then the pH was adjusted to 7.9 with 6-N sulfuric acid. Four hundred grams of this do e were diluted to 800 cc. with distilled water and made acid to Congo red with 20 per cent hydrobromic acid. The precipitate was filtered and extracted with absolute ethyl alcohol until bromide-free. The product was then dried in vacuum. The yield was 11.5 grams. This was dispersed as described in Example 9. I

Example ]2.--Styrei1e N-butyl maleamic acid interpolymer Forty and fourtenths grams of styrene-maleic anhydride interpolyrner (inherent viscosity, 0.68) were dispersed with shaking 4C4 cc. of dry methyl ethyl ltetone. To the dope was added with stirring a solution of 14.6 grams of n-butylamine in 404 cc. of dry methyl ethyl liC-iOllfii. There was instant precipitation. The mixture was well shaken and left at room temperature for .7 hours. The polymer had then precipitated as a cake which was broken up and to the mixture was added 50 cc. of 28 per cent ammonium hydroxide. The eaction mixture was then allowed to'stand for 5- hours. The precipitate was then filtered, reexlract d with methyl ethyl ketone and dried in vacuum. The yield was 64 urns.

Forty grams of this polymer were dispersed in 1000 cc. of distilled water to which had been added cc. of 28 per cent ammonium hydroxide. Solution occurred. The dope was diluted to 1 00 grams, in: ting concentr tion of 2.5 per cent in solids. The pl-i las 9.0.

To isolate the acid form of the polyn e 400 grams of .'s dope diluted with an equal part of water were made red to Congo red with 20 per cent hydrobromic acid. The precipitate was '"ltered, extracted with water until died in vacuum. he yield was 7 tion of this prcci was redispersed in Wu. y .no addition of ammonium hydroxide, it was found to yield packets.

Example I3.--POZystyrene-N-dietlzyl maleic acid olated nude-free. The product was then dried in a vacuum desiccator under constant Water pump vacuum.

To prepare the ammonium salt of the polystyrene 1*- diethyl maleamic acid, 10 grams of the acid polymer were added to 75 ml. of w ter 1th stirring by a. mixer. Twenty-eight per cent NHAOH was added portionwise to keep the pH at about 3. After 12 hours stirri g 2. light amber dope was obtained. This dope was filtered and diluted to 6.66 per cent solids, pH 8.33.

Example 14.C0poiymer 0 styrenemcry[amide:acrylic acid The following were put in an all-glass reflux outfit:

52 grams styrene 5 g ams acrylemide 36 grams acrylic acid 1.225 grams benzoyl peroxide 367.5 grams absolute ethyl alcohol Example 15 Separate red-sensitive and green-sensitive silver bromoiodide emulsions were made containing 33 grams of gelatin per grams of silver halide.

The smooth dope obtained was A cyan Coupler dispersion was made by dissolving 4.375 grams of the coupler 2-[ot-(2,4-di-tert.-arnylphenoxy)-n-butyrylamino]-4,6-dichloro--methyl phenol and 0.27 gram of dioctyl hydroquinone in 5 cc. of n-butyl phthalate at 150 C. adding the solution to 5 cc. of a 5% solution of Alkanol B dispersing agent in 25 cc. of gelatin solution, and dispersing it therein.

A magenta coupler dispersion was made by dlSSOlVlIlg 2.75 grams of the coupler l-(p-p'-tert.-butyl-phenoxyphenyl) 3 [m.-(p-tert.-amylphenoxy)benzoylaminol- S-pyrazolone and 0.21 gram of dioctyl hydroquinone 1n 7.9 cc. of n-butylphthalate at 165 0., adding the solution to 5 cc. of a 5% solution of Alkanol B in 25 cc. of 10% gelatin solution, and dispersing it therein.

Six grams of the red-sensitive emulsion containing 0.4 gram of silver halide and 0.13 gram of gelatin were added to 8 grams of the cyan coupler dispersion and mixed with a fast stirrer for 10 minutes. Twelve cc. of a 10% solution of a copolymer of methacrylic acid and methyl-a-methacrylate (sodium salt) were mixed with 100 cc. of distilled water. The emulsion-coupler dispersion was added to the copolymer solution, and this was stirred for 10 minutes more. To this mixture there were added 4 cc. of a 0.5% solution of the ammonium salt of styrenemaleamic acid polymer, and the Whole dispers1on was stirred at 42" C. for one hour. Then 50 cc. of an 18% solution of gelatin were added and mixed.

A similar dispersion was made using 6 grams of the green-sensitive emulsion containing 0.4 gram of silver halide and 0.13 gram of gelatin, and 8 grams of the magenta coupler dispersion instead of the red-sensitive emulsion and cyan coupler.

The two final dispersions were mixed together and coated, and after exposure and development in a p-phenylene-diamine type color developer, gave satisfactory cyan and magenta images in the portions exposed to red and green light, respectively.

A three-color emulsion was made as follows:

Example 16 A yellow-forming coupler dispersion was made by first dissolving 5 grams of the coupler N-(p-benzoyl acetamino benzene sulfonyl)-N-('y-phenylpropyl)-p-toluidine and 0.21 gram of dioctyl hydroquinone in 8 grams of dibutyl phthalate at 140150 C. This solution was added to 25 grams of 10% gelatin solution containing 5 cc. of a 5% solution of Alkanol B dispersing agent and the mixture stirred for five minutes. Six grams of a concentrated gelatino-silver bromoiodide emulsion .containing 2.04'

grams of silver halide and 0.095 gram of gelatin were then added to 8 grams of the coupler dispersion and the mixture stirred for minutes at 40 C. The mixture was then added to 12 cc. of a 10% solution of a copolymer of methacrylic acid and methyl-wmethacrylate (sodium salt) in 100 cc. of water which had been stirred at 40 C. for 10 minutes. To this mixture there were added 5 cc. of a 0.5% solution of the ammonium salt of styrenemaleamic acid polymer and the whole dispersion was stirred for 12 minutes more. The mixture was then added to 50 grams of an 18% gelatin solution.

A cyan-forming coupler dispersion was made by dissolving 3.5 grams of the coupler 2-[a-(2',4-tert.-amylphenoxy)-n-butyryl amino], 4,6-dichloro-5-methylphenol and 0.21 gram of dioctyl hydroquinone in 8 grams of dibutyl phthalate at 140150 C. This solution wasadded to 25 grams of a 10% solution of gelatin containing 5 cc. of a 5% solution of Alkanol B and was stirred for five minutes. added to 5.25 grams of a red-sensitive 95 mole per cent chloride, silver chlorobromide emulsion containing 1.24 grams of silver halide and 0.43 gram of gelatin, prepared by adding 5 milligrams'of the red sensitizer, 5 [4-(3-ethyl- 2- (3 -benzothiazolylidene) -2-butenylidene1 -3-n-heptyl lphenyl-Z-thiohydantoin (U. S. Patent 2,282,116) in 8 cc; of acetone to 66 grams of the emulsion, and the mixture was stirred for 15 minutes at 40 C. The mixture was then added to 12 grams of a 10% solution of a copolymer of methacrylic acid and methyl-a-methacrylate (sodium salt) in 100 cc. of water which had been stirred for 15 minutes at 40 C. The mixture was stirred for 10 minutes at 40 C. and to it was added 5 cc. of a 0.5 solution of the ammonium salt of styrene-maleamic acid polymer and the mixture was stirred for 10 minutes more.

Eight grams of this coupler dispersion were.

10 It was then added to 50 cc. of an 18% gelatin solution and mixed.

A magenta-forming coupler dispersion was made by first dissolving 2.75 grams of the coupler, 1-[p-(p'-tert.- butyl-phenoxyl) phenyl] 3 [m-(p-tert.- amylphenoxy)- benzoylamino]-5-pyrazolone and 0.21 gram of dioctohydroquinone in eight grams of dibutyl phthalate at C. This solution was added to 25 cc. ofa 10% gelatin solution containing 5 cc. of a 5% solution of Alkanol B and was stirred for five minutes. Eight grams of this dispersion were added to 5.25 grams of a greensensitive 95 mole per cent chloride, silver chlorobromide emulsion containing 1.24 grams of silver halide and 0.43 gram of gelatin made by sensitizing 66 grams of the emulsion with 7 /2 milligrams of the green-sensitizer 5-[(1-ethyl-2-(3 )-ot-naphthoxazolylidene)-ethylidenel 3 n heptyll-phenyl-2-thiohydantoin (U. S. Patent 2,282,116) in 10 cc.'of methanol. This mixture was then added to a solution of a copolymer of methacrylic acid and methyl-amethacrylate (sodium salt) and a solution of the ammonium salt of styrene-maleamic acid polymer in the same way as the red-sensitive emulsion described above.

To produce a three-color coating, 60 grams of each of the blue-sensitive, green-sensitive and red-sensitive components were mixed with stirring. The mixture was then coated in the usual manner on a paper support and dried. After exposure and development in a developing solution containing 2-amino-5-diethyl amino toluene hydrochloride as the developing agent, colored images complementary to the color of the exposing light were formed in the emulsion.

I claim:

1. A light-sensitive mixed packet photographic emulsion comprising packets or discrete particles of gelatin reacted with a water-soluble salt of an interpolymer of styrene and an a,,8-unsaturated carboxylic acid, said particles or packets containing a non-difiusing color-forming compound capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, and silver halide sensitive to at least one region but less than all regions of the visible spectrum, and at least one separate set of packets or dis crete particles of gelatin reacted with said interpolymer containing a non-diffusing color-forming compound dilferent from said first mentioned color-forming compound and silver halide sensitive to a region of the visible spectrum diiferent from that to which said first mentioned silver halide is sensitive, the sensitive and color-forming ingredients being within the respective packets or discrete particles and all of said packets or discrete particles being dispersed in gelatin having mixed therewith a watersoluble salt of a polymer selected from the class consisting of methylmethacrylate-methacrylic acid copolymer, algin, carboxy methyl cellulose and cellulose sulfate.

2. A light-sensitive mixed packet photographic emulsion comprising packets or discrete particles of gelatin reacted with the ammonium salt of a styrene-maleamic acid polymer, said particles or packets containing a nondiffusing color-forming compound capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, and silver halide sensitive to at least one region but less than all regions of the visible spectrum and at least one separate set of packets or discrete particles of gelatin reacted with said polymer, containing a non-difiusing color-forming compound diiferent from said first mentioned color-forming'compound and silver halide sensitive to a region of the visible spectrum different from that to which said first mentioned silver halide is sensitive, the sensitive and color-forming ingredients being within the respective packets or discrete particles and all of said packets being dispersed in gelatin having mixed therewith the sodium salt of methylmethacrylate methacrylic acid copolymer.

3. A photographic element comprising a support having thereon a single light-sensitive water-permeable colloid layer containing (1) packets or discrete particles of gelatln reacted with the ammonium salt of a styrene-maleamic acid polymer, said particles or packets containing a nondiflusing yellow-forming coupler and blue-sensitive silver halide, (2) packets or discrete particles of gelatin reacted with the ammonium salt of a styrene-maleamic acid polymer, said particles or packets containing a non-diffusing magenta-forming coupler and green-sensitive silver halide, and (3) packets or discrete particles of gelatin reacted with the ammonium salt of a styrene-maleamic acid polymer, said particles or packets containing a nondut'using cyan-rorming coupler and red-sensitive silver halide, and said colloid layer having mixed therewith the sodium salt or" methylmethacrylate-methacrylic acid copolymer.

4. lbs method or making a mixed packet photographic emulsion which comprises dispersing in a gelatino-sllver halide emulsion sensitive to at least one but less than all regions of the visible spectrum, a non-dilrusing colorforming compound capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development to form a dispersion or' the color-forming compound in the emulsion, mixing said dispersion with rrom about one part to about two parts per part of gelatin in said emulsion, of a water-soluble salt or' a polymer selected from the class consisting of methylmethacrylate-methacrylic acid copolyrner, algin, carboxy methyl cellulose and cellulose sulrate, adding to the mixture of dispersion and polymer slowly and with stirring a solution or a water-soluble salt of an interpolymer of styrene, said interpolymer containing at least a carboxylic acid group of the groups selected item the class consisting of carboxylic acid and carboxylic acid amide groups to form a dispersion of particles of gelatin, water-soluble salt of styrene interpolymer and silver halide, containing the color-forming compound, forming in the same way as said last-mentioned dispersion at least one other dispersion of particles of gelatin, water-soluble salt of styrene mt rpolymer, diilereht non-diffusing colorforming compound and silver halide sensitive to a region of the visible spectrum different from that to which said first-mentioned silver halide is sensitive, in each of said dispersions said water-soluble polymer beng used in an amount from about 1 to about 2 times the amount of gelatin, and said water-soluble salt of styrene interpolymer being used in an amount less than about one-ha the amount of gelatin, and mixing said dispersions of particles with a gelatin solution.

5. The method of making a mixed packet photographic emulsion which comprises mixing a non-di'rrusing colortorming compound capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, with a substantially Water-insoluble solvent for said color-forming compound to form a solution of the color-forming compound in the solvent, dispel 'ng the solution in a gelatino-silver halide emulsion sensitive to at least one but less than all regions of the visible spectrum, mixing said dispersion with from about one part to about two parts per part of gelatin in said emulsion, of a water-soluble salt of a polymer se lected from the class consisting of methylmethacrylatemethacrylic acid copolymer, algin, carboxy methyl cellulose and cellulose sulfate, adding to the mixture of dispersion and polymer slowly and with stirring a solution of a water-soluble salt of an interpolymer of styrene, said interpolymer containing at least a carboxylic acid group of the groups selected from the class consisting of carboxylic acid and carboxylic acid amide groups to form a dispersion of particles of gelatin, water-soluble salt of styrene inter-polymer and silver halide, containing the color-forming compound, forming in the same way as said last-mentioned dispersion at least one other dispersion of particles of gelatin, Water-soluble salt of styrene interpolymer, diiferent non-diffusing color-forming compound and silver halide sensitive to a region or" the visible spectrum different from that to which said first-mentioned silver halide is sensitive, in each of said dispersions said water-soluble polymer being used in an amount from about 1 to about 2 times the amount of gelatin, and said water-soluble salt of styrene interpolymer being used in an amount less than about one-half the amount of gelatin, and mixing said dispersions of particles with a gelatin solution.

sphic mixed packet dispersion, the continuous phase comprising'an aqueous colloidal binder and the disperse phase comprising at least two dilferently light-sensitive sets of packets or discrete particles, each packet of any one set itself containing dispersed therein silver halide grains sensitized to one of the primary regions of the visible spectrum and also containing dispersed therein non-diffusing color-forming compound capable of reacting with the oxidation product of a primar. aromatic amino develo in" a ent on hoto ra hic development, the particles of any one set being formed when a water-soluble salt of a styrene interpolymcr containing carboxylic acid groups is added in the presence or a water-soluble salt of methyl methacrylate-methacrylic acid, 0 a silver halide dispersion peptized by gela- Llii, the styrene intcrpolymer-gelatin combination which forms the continuous phase or' the packets being immiscible with ""d aqueous colloidal binder.

7. thod of making mixed packet photographic s mixn a non-diltusing colore of reacting with the oxida- J aromatic amino developing agent on photographic cu, elo ment, with a substantially *r-insoluole solvent for color-forming compound to orm a soiut n of the color-forming compound in the solvent, u" ersing the solution in a gelatino-silver halide emulsion sensitive to at least one region but less than all regions of the visible spectrum, mixing said dispersion with frorut 2 parts of the sodium sa thacryiic acid copolyrner, persion and polymer SiG'fi/i on of a polymeric car oxyi groups form a dlSl rsion e to at least one region but less of the visible spectrum, mixing said dis- "Ct LIIUTT'Z t of methyl-methacrylate thacrylic acid coadding he .nixture of di persion and polyy and w "tirringa solution of styrene interxyl roups on the polymeric chain, to form at. spe s of gelatin, interpolymer and silver halide .ainingthc color-forming compound, the same way said lastmentioned dispersion, at least one other dispersion of particles of gelatin,

interpolymer, different non-dillusing color-forming compound ant ilver "lide sensitive to a region of the visible spect 1, di rent from that to which firstsilver halide is sensitive, in each of said disd copolymcr being used in an amount from about 2 times the am int of gelatin, and said interpolymers being used in than onehalf the amount of g n, and mixing said dispersions solution.

'xed packet photographic g a non-diffusing coloring with the oxidadeveloping ubstantially o,- rming compound to form a solution. oi the color-forming compound in the solvent, disp rs ng the solu lino-silver is: emulsion sen it less g said dis- ,rts of the e moth/acrylic acid conixture of dispersion and polyh stirring solution of interpolymer an u,/-unsaturated carboxylic acid to 1 Suki sod :1 salt of ne'r, adding to slowly a d of styrene a form dim of "rticles of gelatin, interpolymer and silver contai the color-forming compound,

forming in the same may as said last-mentioned dispersion, at least one other dispersion of particles of gelatin, interpolymer, different non-diffusing color-forming compound and silver halide sensitive to a region of the visible spectrum diiferent from that to which said firstmentioned silver halide is sensitive, in each of said dispersions said water-soluble polymer being used in an amount from about 1 to about 2 times the amount of gelatin, and said interpolymer being used in an amount less than one-half the amount of gelatin, and mixing said dispersions of particles with a gelatin solution.

10. A light-sensitive mixed packet photographic emulsion comprising packets or discrete particles of gelatin reacted with a water-soluble salt of an interpolymer of styrene, said interpolymer containing at least a carboxylic acid group of the groups selected from the class consisting of carboxylic acid and carboxylic acid amide groups, said particles or packets containing a non-diffusing colorforming compound capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, and silver halide sensitive to at least one region but less than all regions of the visible spectrum, and at least one separate set of packets or discrete particles of gelatin reacted with said interpolymer, containing a non-diffusing color-forming compound difierent from said first-mentioned color-forming compound and silver halide sensitive to a region of the visible spectrum different from that to which said first-mentioned silver halide is sensitive, the sensitive and color-forming ingredients being within the respective packets or discrete particles and all of said packets or discrete particles being dispersed in gelatin and having mixed therewith the sodium salt of methylmethacrylate-methacrylic acid copolymer.

11. A light-sensitive mixed packet photographic emulsion comprising packets or discrete particles of gelatin reacted with the ammonium salt of styrene-acrylamideacrylic acid interpolymer, said particles or packets containing a non-difiusing color-forming compound capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, and silver halide sensitive to at least one region but less than all regions of the visible spectrum, and at least one separate set of packets or discrete particles of gelatin reacted with said interpolymer, containing a non-diffusing color-forming compound diflrerent from said first-mentioned color-forming compound and silver halide sensitive to a region of the visible spectrum difierent from that to which said first-mentioned silver halide is sensitive, the sensitive and color-forming ingredients being within the respective packets or discrete particles and all of said packets or discrete particles being dispersed in gelatin and having mixed therewith the sodium salt of methylmethacrylate-methacrylic acid copolymer.

References Cited in the file of this patent UNITED STATES PATENTS 1,976,679 Fikentscher Oct. 9, 1934 2,284,877 Martinez June 2, 1942 2,399,084 Watson Apr. 23, 1946 2,490,749 Fierke et al Dec. 6, 1949 2,548,526 Godowsky Apr. 10, 1951 2,565,418 Yackel Aug. 21, 1951

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Classifications
U.S. Classification430/549, 525/327.6, 430/550, 430/546, 430/365, 430/531, 430/536, 430/569, 526/304, 524/23, 525/327.8, 524/22, 526/272, 524/24, 430/383, 525/374
International ClassificationG03C7/388
Cooperative ClassificationG03C7/3882
European ClassificationG03C7/388P