US3573049A - Photographic materials and processes for developing photographic compositions having a zwitterionic and anionic elements - Google Patents

Abstract

PHOTOGRAPHIC COMPOSITIONS AND ELEMENTS COMPRISING A ZWITTERIONIC COMPOUND AND AN ANIONIC COMPOUND. IN ONE ASPECT, THIS INVENTION RELATES TO A PROCESS COMPRISING DEVELOPING A PHOTOGRAPHIC IMAGE IN THE PRESENCE OF A ZWITTERIONIC COMPOUNDAND AN ANIONIC COMPOUND. IN ANOTHER ASPCT, THIS INVENTION RELATES TO A PHOTOGRAPHIC DEVELOPER COMPOSITION COMPRISING A PHOTOGRAPHIC DEVELOPING AGENT, A SWITTERIONIC COMPOUND, AND AN ANIONIC COMPOUND.

Description

United States Patent 3,573,049 PHOTOGRAPHIC MATERIALS AND PROCESSES FOR DEVELOPING PHOTOGRAPHIC COMPOSI- TIONS HAVING A ZWITTERIONIC AND ANHONIC ELEMENTS Norman W. Kalenda, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y. No Drawing. Filed Oct. 2, 1967, Ser. No. 671,955 Int. Cl. G03c 5/30 US. Cl. 96-663 20 Claims ABSTRACT OF THE DISCLOSURE Photographic compositions and elements comprising a zwitterionic compound and an anionic compound. In one aspect, this invention relates to a process comprising developing a photographic image in the presence of a zwitterionic compound and an anionic compound. In another aspect, this invention relates to a photographic developer composition comprising a photographic developing agent, a zwitterionic compound, and an anionic compound.

This invention relates to novel photographic materials and their preparation and to novel photographic processes. In one aspect, this invention relates to a means for reducing fog in photographic emulsions and elements which contain a zwitterionic compound. In another aspect, this invention relates to photographic emulsions, elements and processes in which zwitterionic compounds are used in combination with anionic compounds.

It is known to use certain zwitterionic compounds as wetting agents to produce photographic emulsions having improved wetting characteristics. In US. Pat. 2,197,809 of McQueen, granted Apr. 23, 1940, various cation-active surface active compounds including certain betaines are incorporated in photographic emulsions to give more thorough wetting of the emulsion during development. Zwitterionic compounds have also been used as coating aids. In U.S. Pat. 3,133,816 of Ben-Ezra, granted May 19, 1964, certain betaines are used in combination with certain amino acids as a coating solution for photographic materials. However, many of these zwitterionic surfactants strongly increase development fog and tend to produce high fog on storage.

Thus, it is an object of this invention to provide new photographic compositions.

Another object of this invention is to provide novel photographic emulsions and elements which comprise a zwitterionic compound and which have reduced fog on development and incubation.

A further object of this invention is to provide photographic emulsions and elements which have improved wettability.

Still another object of this invention is to provide photographic emulsions and elements which have lower surface resistivity.

Another object of this invention is to provide novel developer compositions and novel processes for developing photographic emulsions and elements which result in reduced fogging.

Other objects will be apparent from the specification and claims.

It has been found that these and other objects are accomplished by using a zwitterionic compound in combination with an anionic compound in photographic emulsions, elements and processes. The use of the anionic compound with the zwitterionic compound makes it possible to obtain the advantages of the zwitterionic compounds in photographic applications without the increases in fog often associated with the use of the Zwitterions 3,573,049 Patented Mar. 30, 1971 alone. The Zwitterions and anions of the invention can be contained in a photographic emulsion or element, as well as in a processing solution or element, and can be combined individually or together with a photographic developing agent in a photographic developer composition. The zwitterionic compound and the anionic compound can be contained in the same or in different layers in a photographic element.

The zwitterionic compounds employed in the practice of this invention are compounds which contain both a negatively and a positively charged atom in each molecule. Zwitterions are also sometimes referred to as inner salts. These Zwitterions can be represented generically as compounds having the formula C BA wherein C represents an organic cationic residue and BA repre sents the covalently bound anionic part of the molecule in which A can be an anionic acid residue such as, for example, carboxylate (--CO sulfonate (SO sulfate (-OSO and the like. The Zwitterions can be used in the form of adducts with protonic acids.

Typical zwitterionic compounds which are useful in this invention include betaines such as:

( IO-carboxydecyl) dimethyldodecylammonium hydroxide, inner salt,

(Z-carboxy-i-butyl dimethyldodecylammonium hydroxide, inner salt,

(2-carb oxyethyl) dimethyldodecylammonium hydroxide, inner salt,

(2-carb oxymethyl) dimethyldodecylammonium hydroxide, inner salt,

(3-sulfopropyl)dimethyldodecylamrnonium hydroxide, inner salt,

(4-sulfobutyl)dimethyldodecylammonium hydroxide, inner salt,

(3-sulfobutyl) dimethyldodecylammonium hydroxide, inner salt,

(3 -sulfopropyl) diethyldodecylammonium hydroxide, inner salt,

(4-sulfobutyl) diethyldodecylammonium hydroxide, inner salt,

( 2-carboxyethyl) dimethyloctadecylammonium hydroxide, inner salt,

(carboxymethyl) dimethyloctadecylamrnonium hydroxide, inner salt,

(3-sulfopropyl)dimethyloctadecylammonium hydroxide, inner salt,

pyridinium betaines, such as:

1-(l-carboxytridecyl)pyridinium hydroxide, inner salt, 1-(l-carboxyundecyl)pyridinium hydroxide, inner salt, 1-(10-carboxydecyl)pyridinium hydroxide, inner salt, 1-(10-sulfatodecyl)pyridinium hydroxide, inner salt, 3-carbethoxy-1-(10-carboxydecyl)pyridinium hydroxide, inner salt, l-(17-carboxy-6-oxo-7-azaheptadecyl)pyridinium hydroxide, inner salt, 3-carboxy-l-dodecylpyridinium hydroxide, inner salt,

thetins, such as:

( l-carboxyethyl) methyldodecylsulfonium hydroxide,

inner salt,

(Z-carboxyethyl)methyldodecylsulfonium hydroxide,

inner salt,

(3-sulfopropyl)methyldodecylsulfonium hydroxide,

inner salt,

(2-carboxyethyl)methylhexadecylsulfonium hydroxide,

inner salt,

( l-carboxyethyl)methylhexadecylsulfonium hydroxide,

inner salt,

(2-carboxy-i-butyl)methyldodecylsulfonium hydroxide,

inner salt,

3 10-carboxydecyl tetrahydrothiophenium hydroxide,

inner salt,

and the like.

A preferred class of zwitterionic compounds useful in the practice of this invention are the sulfobetaines. Sulfobetaines are zwitterionic compounds which have a positively charged nitrogen atom and have a sulfonate group (-80 in the covalently bound anionic part of the molecule. Sulfobetaines can be generally represented by the following formula:

wherein R R and R can be unsubstituted or substituted alkyl or aryl groups, such as methyl, ethyl, propyl, 2- methylpropyl, decyl, hexadecyl, hydroxyethyl, benzyl, and the like, and phenyl, naphthyl, tolyl and the like; and two or more of the groups R R or R can be taken together to form a heterocyclic ring having one or more hetero atoms; R, is an unsubstituted or substituted alkyl chain containing one or more carbon atoms, such as a methyl, ethyl, pentyl, Z-methylpropyl and decyl chain and the like.

Typical sulfobetaines useful in this invention include:

(3-sulfopropyl) dimethyldodecylammonium hydroxide,

inner salt,

(4-sulfobutyl) dimethyldodecylammonium hydroxide,

inner salt,

(3-sulfobutyl) dimethyldodecylammonium hydroxide,

inner salt,

(3-sulfopropyl diethyldodecylammonium hydroxide,

inner salt,

(4-sulfobutyl)diethyldodecylammonium hydroxide,

inner salt,

(3-sulfopropyl dimethylo ctadecylammonium hydroxide, inner salt,

and the like.

Sulfobetaines are generally prepared by reacting a tertiary amine with a sulfone or by quaternizing a tertiary aminoalkylene sulfonate. For example,

SOaR

l SOa a carboxylate (CO and the like. In one embodiment, these acidic substituents can be contained in monomers which are reacted to form a polymer or can be added to a polymeric molecule during or after the polymerization reaction. In one preferred embodiment, the anionic acidic substituent is a sulfoxy substituent, a radical which has at least one sulfur atom and at least one oxygen atom and which has a net negative charge. Typical anionic compounds which are useful in the invention include polyalkylene glycol ether sulfates, poly(sulfoalkylacrylates), for example, such as those disclosed in Belgian Pat. 679,412 issued Oct. 12, 1966, carboxylated fatty alcohols and the like. In a preferred embodiment of the invention the zwitterionic compound is (3-sulfopropyl)dimethyldodecylammonium hydroxide, inner salt, and the anionic compound is the ammonium salt of dodecyl phenyl polyethylene glycol ether sulfate or copoly(butyl acrylatesulfopropyl acrylate).

In one embodiment, when the anionic compounds such as, for example, polyethylene glycol ether sulfates are used with the sulfobetaines such as (3-sulfopropyl)dimethyldodecyl ammonium hydroxide, inner salt, processed coatings having higher wettability and unprocessed coatings having lower surface resistivity are obtained as r well as a reduction in fogging. Higher wettability reduces the tendency of water droplet formation on the surface of the emulsion thus reducing water spotting during drying of the emulsion. Lower surface resistivity will diminish problems resulting from static electricity in the film such as incidental visible electrical discharges which leave latent images in the photographic emulsion.

In a preferred embodiment of this invention, the photographic elements contain silver halide emulsions. The silver halide, the zwitterionic compound and the anionic compound can be contained in the same layer or in different layers of a photographic element. The preferred concentration of the zwitterions in the silver halide emulsions and in elements of the invention is from about 0.50 to 50 grams per mole of silver in the silver halide layer and is generally from about 1.0 to 30 grams per mole of silver in the silver halide layer. The preferred concentration of the anionic compound in the silver halide emulsions and elements of the invention is from about 5 milligrams to 25 grams per mole of silver in the silver halide layer, and is generally from about 0.1 to 10 grams per mole of silver in the silver halide layer.

Any suitable photographic developing agent can be used in the developer compositions of this invention. Typical developers include polyhydroxybenzenes such as hydroquinone, pyrogallol, catechol, and the like, ascorbic acids, 3-pyrazolidones, p-aminophenols, phenylenediamines, and the like. The developer compositions of the invention comprise a photographic developing agent and generally from about 1.0 to 50 grams per liter of the developer composition of a zwitterionic compound and from about 50 milligrams to 25 grams per liter of the developer composition of an anionic compound. Furthermore, the zwitterionic compound can be contained in an emulsion while the anionic compound is in a processing solution or element, and similarly the anion can be contained in an emulsion while the zwitterion is in a processing solution or element.

The new developer compositions according to this invention can be provided in kit form as long as the essential ingredients are present, namely the developer, the zwitterionic compound and/or the anionic compound. The kit may comprise diluted, concentrated or powdered forms of said ingredients individually packaged or combined together, which can be used to form an aqueous bath of said ingredients. The compounds are generally provided individually in a form which can be added to water just prior to using the developer bath.

The emulsion can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including for example, stabilizers or antifog gants, particularly the water-soluble inorganic acid salts of cadmium, cobalt, manganese and zinc as disclosed in U.S. Pat. 2,829,404, the substituted triazaindolizines as disclosed in U.S. Pats. 2,444,605 and 2,444,607, speed increasing materials, absorbing dyes, plasticizers and the like. Suitable hardeners which can be used include, for example, formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides. Sensitizing dyes useful in sensitizing such emulsions are described, for example, in U.S. Pats. 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, 1950. Sensitizers which give particularly good results in the photographic compositions disclosed herein are the alkylene oxide polymers which can be employed alone or in combination with other materials, such as quaternary ammonium salts, as disclosed in U.S. Pat. 2,886,437 or with mercury compounds and nitrogen containing compounds as disclosed in U.S. Pat. 2,751,299. Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.

Various silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide. The silver halides preferably used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide crystals such as described in U.S. Pat. 2,592,250 of Davey and Knott issued Apr. 8, 1952. Particularly useful are high contrast photographic emulsions of the type described in U.S. Pat. 2,756,148 of MacWilliams, granted July 24, 1956.

The silver halide emulsion layer of a photographic element which is useful in the instant invention can contain any of the hydrophilic, water permeable binding materials suitable for this purpose. Suitable materials include gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these binding agents can also be used. The binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized vinyl compounds. Such compounds are disclosed, for example, in U.S. Pats. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July 6, 1965; 3,062,674 of Houck et al. issued Nov. 6, 1962 and 3,220,844 of Houck et al. issued Nov. 30, 1965; and include the water insoluble polymers of alkyl aerylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.

emulsions useful in the instant invention can be further enhanced by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Pat. 3,011,890 of Gates, Jr., et al. issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. 635,206 of Koller et al. issued Jan. 23, 1962.

The photographic elements prepared according to the instant invention can be used in various kinds of photographic systems. In addition to being useful in X-ray and other nonoptically sensitized systems, they can also be used in orthochromatic, panchromatic and infrared sensitive systems. The sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.

Silver halide emulsions useful in the instant invention can be sensitized using any of the well known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/ or gold compounds. The emulsions can also be sensitized with salts of noble metals of Group VIII of the Periodic Table which have an atomic weight greater than 100.

This invention can be further illustrated by the following examples of preferred embodiments thereof although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.

EXAMPLE 1 A large grain silver bromoiodide emulsion having 473 mg. of silver per square foot and 350 mg. of gelatin per square foot and a gelatin overcoat having 130 mg. of gelatin per square foot are coated onto a poly(ethylene terephthalate) support. The anionic compounds of Table I and the zwitterion (3-sulfopropyl)dimethyldodecylammonium hydroxide, inner salt, are each coated in a gelatin overcoat at 7.5 mg. per square foot. The coatings are exposed on an Eastman IB Sensitometer and developed for six minutes in an Elon-hydroquinone developer.

Wettability is determined by measuring the surface area of the emulsion covered by one milliliter of distilled water.

Using the following anionic compounds:

(A) ammonium salt of dodecylphenylpolyethylene glycol ether sulfate, and (B) copoly (butylacrylate-sulfopropylacrylate the following results were obtained:

The silver halide emulsion of a photographic element which is useful in the instant invention can be coated on a wide variety of supports. Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyester film supports such as poly- (ethylene terephthalate) and related films or resinous materials as well as glass, paper, metal and the like. Supports such as paper which are coated with u-olefin polymers, particularly polymers of u-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers and the like can also be employed.

The sensitometric characteristics of the photographic propyl)dimethyloctadecylammonium hydroxide, inner salt, (l-carboxyethyl) methyldodecylsulfonium hydroxide, inner salt, and (4-sulfobutyl)dimethyldodecylammoninum hydroxide, inner salt, are tested in the same manner, similar results are obtained. Similar results are also obtained when the zwitterionic compounds and anionic compounds are used in the developing composition.

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

I claim:

1. A photographic element comprising (1) a support, (2) at least one layer coated thereon containing a photographic silver halide composition, (3) at least one layer coated thereon which contains a zwitterionic compound and (4) at least one layer coated thereon which contains at least 5 milligrams of anionic surfactant per mole of silver in said layer containing silver halide.

2. A photographic element according to claim 1 wherein said layer containing silver halide comprises at least 0.50 gram of said zwitterionic compound per mole of silver and at least 5 milligrams of an anionic surfactant per mole of silver.

3. A photographic element according to claim 1 wherein said anionic surfactant has at least one anionic acid substituent.

4. A photographic element according to claim 3 wherein said anionic substituent is a sulfate group, a sulfonate group or a sulfoxylate group.

5. A photographic element according to claim 1 wherein said layer containing silver halide further comprises gelatin.

6. A photographic element according to claim 1 wherein said zwitterionic compound is a sulfobetaine.

7. A photographic element according to claim 1 wherein said zwitterionic compound is (3-sulfopropyl)dimethyldodecylammonium hydroxide, inner salt.

8. A photographic element according to claim 1 wherein said anionic surfactant is a polyalkylene glycol ether sulfate.

9. A photographic element according to claim 1 wherein said anionic surfactant is a poly(sulfoalkylacrylate).

10. A photographic element according to claim 1 wherein said zwitterionic compound is (sulfopropyl)din1ethyldodecylammonium hydroxide, inner salt, and said anionic surfactant is the ammonium salt of dodecylphenylpolyethylene glycol ether sulfate.

11. A photographic element according to claim 1 where- 8 in said zwitterionic compound is (3-sulfopropyl)dimethyldodecylammonium hydroxide, inner salt, and said anionic surfactant is copoly(butylacrylate-sulfopropyl acrylate).

12. A photographic composition comprising a gelatinous, light-sensitive, silver halide emulsion, at least 0.50 gram per mole of silver of a zwitterionic surfactant and at least 5 milligrams of an anionic surfactant per mole of silver.

13. A photographic composition according to claim 12 wherein said anionic surfactant comprises sulfate groups, sulfonate groups or sulfoxylate groups.

14. A photographic composition according to claim 12 wherein said zwitterionic surfactant is a sulfobetaine compound.

15. In a process for producing an image in a photographic element containing at least one layer which comprises a silver halide composition, the improvement comprising developing said silver halide composition in the presence of a zwitterionic compound and an anionic surfactant.

16. A process according to claim 15 wherein said zwitterionic compound is a sulfobetaine and said anionic surfactant contains sulfate groups, sulfonate groups or sulfoxylate groups.

17. A photographic developer composition comprising a silver halide developing agent, at least about 1.0 gram per liter of a zwitterionic compound and at least about milligrams per liter of an anionic surfactant.

18. The developer composition of claim 17 wherein said zwitterionic compound is a sulfobetaine.

19. The process of claim 17 wherein said anionic surfactant is a polymer having at least one anionic acidic substituent.

20. A kit comprising the ingredients for providing said composition of claim 17.

References Cited UNITED STATES PATENTS 2,719,087 9/1955 Knox et al. 96114.5 2,922,690 1/ 1960 Mueller et al. 8-21 3,113,026 12/1963 Sprung 96107 OTHER REFERENCES Moilliet, J. L.: Surface Activity, Van Nostrand, 1961.

NORMAN G. TORCHIN, Primary Examiner J. L. GOODROW, Assistant Examiner US. Cl. X.R. 96114.5