US3833372A

US3833372A - Viscous developing liquid for use in a silver salt diffusion transfer process

Info

Publication number: US3833372A
Application number: US00305027A
Authority: US
Inventors: K Hayashi; R Ohi; T Shishido
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1971-11-09
Filing date: 1972-11-09
Publication date: 1974-09-03
Anticipated expiration: 1991-09-03
Also published as: GB1378398A; DE2254873A1; JPS5436495B2; JPS4854937A

Abstract

A silver halide-containing viscous developing liquid to be used in a diffusion transfer process comprising an hydroxylamine type developing agent, a sulfur-free nitrogen-containing silver halide solvent, a cellulose derivative thickener, an alkali agent and a color modifying or toning agent of at least one compound represented by the following formulae (I), (II) and (III):

(wherein R1, R2 and R3 are a hydrogen atom, an alkyl or substituted alkyl group containing 1-4 carbon atoms, or a phenyl group, m is an integer of 2-4, and n is 0 or an integer of 1-4).

Description

United States Patent [1 1 Hayashi et al.

[451 Sept. 3, 1974 1 VISCOUS DEVELOPING LIQUID FOR USE IN A SILVER SALT DIFFUSION TRANSFER PROCESS [75] Inventors: Katsumi Hayashi; Reiichi Ohi;

Tadao Shishido, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Nov. 9, 1972 [21] Appl. No.: 305,027

[30] Foreign Application Priority Data Primary ExaminerRonald H. Smith Assistant Examiner-John L. Goodrow Attorney, Agent, or Firm-Richard C. Sughrue [57] ABSTRACT A silver halide-containing viscous developing liquid to be used in a diffusion transfer process comprising an hydroxylamine type developing agent, a sulfur-free nitrogen-containing silver halide solvent, a cellulose derivative thickener, an alkali agent and a color modifying or toning agent of at least one compound represented by the following formulae (1), (II) and (III):

(wherein R R and R are a hydrogen atom, an alkyl or substituted alkyl group containing l-4 carbon atoms, or a phenyl group, m is an integer of 2-4, and n is O or an integer of l-4).

33 Claims, No Drawings VISCOUS DEVELOPING LIQUID FOR USE IN A SILVER SALT DIFFUSION TRANSFER PROCESS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the processing of a silver halide light-sensitive material and, in particular, is directed to a developing liquid composition to be used in a transfer diffusion process for a silver halide light-sensitive material.

2. Description of the Prior Art There has heretofore been employed in a silver halide salt diffusion process a negative material prepared by coating a gelatin-silver halide emulsion onto a suitable support in combination with a positive material prepared by coating a solution of colloidal silica (silica gel) or like silver-deposition nuclei on a suitable support.

The developing liquid to be used in a diffusion transfer process with such materials usually contains a developing agent, a silver halide solvent, an alkali agent, an antifogging agent, an antioxidant and a color toning agent.

In this silver salt diffusion transfer process, the exposed silver halide in the negative material is first developed with a developing agent contained in a developing liquid and unexposed silver halide is reacted with a silver halide solvent contained in the developing liquid to form a soluble silver complex salt which diffuses into the positive material and deposits on the silverdeposition nuclei layer to thereby give a silver image.

In a number of diffusion transfer processes known in the art it is advantageous from many viewpoints to use a viscous developing liquid, which is used by spreading the viscous developing liquid at a given thickness between the negative material and the positive material.

When a non-viscous liquid developer is used, processing is usually carried out by putting the exposed negative material over the positive material, and then soaking the combined material in a developing liquid. On the other hand, when a viscous developing liquid is used, the liquid is supplied only to the surfaces of the negative and positive materials so that the developing liquid does not permeate into the supports of the negative material and the positive material. The used of a viscous developing liquid is thus much more advantageous in avoiding contamination, in enabling quick drying and in preventing leaking or spilling as is often encountered in the case when a conventional liquid developer is used, all of which are convenient for portable processing.

However, the use of such a viscous developing liquid does give rise to the following problems. A first problem is that a viscous positive material often results from the residual viscous developing liquid film, which often forms upon stripping off the positive material from the negative material. A second problem is that fouling or discoloration of the print during preservation may result from residual developing liquid which attaches onto the surface of the positive material and contains a developing agent, silver halide solvent, alkali agent and like contaminating materials.

Developing agents heretofore used by the prior art contain, in general, hydroquinone derivatives, p-

aminophenols or 3-pyrazolidones either alone or as combinations thereof, which give dark brown products when they are oxidized. Accordingly, a positive material is liable to be soiled or contaminated by the formation of oxidation products of the developing agent soaked into the layer of the positive material upon stripping the negative material from the positive material.

As a silver halide solvent, a thiosulfate, thiocyanate or thioglycolic acid is usually employed. However, since every compound of this type contains a sulfur atom in the molecule, silver halide solvent which remains attached to the silver image portion reacts with the image silver to form silver sulfide which leads to discoloration.

In order to overcome such defects, it has been proposed to use another type of developing liquid which contains as the main developing agent a compound that forms upon oxidation a colorless or slightly yellow colored oxidation product which has a sufficient reducing ability, e.g., a hydroxylamine, and as the silver halide solvent a sulfur-free compound, e. g., amines such as diethylamine and cyclic imides such as uracil and barbituric acid. This type of developing liquid consisting of hydroxylamine developing agent and a cyclic imide compound, however, has the drawbacks of poor physical developing activity and a slow rate of dissolving silver halide compared to conventional developing liquids comprising a hydroquinone type developing agent and a thiosulfate type solvent. Thus, such materials require a longer processing time than that required upon the use of a conventional developing liquid, i.e., the speed of transfer is lowered a considerable extent.

Moreover, the use of such a developing liquid is subject to another drawback in that yellow or yellowish brown color tones are formed on the positive image silver obtained. In such a case, it is conventional to add a toning or color modifying compound to a processing liquid or to an image receiving layer to make the image color tone neutral or blue-black. A number of toning or color modifying compounds have been used up to now, including for example, l-phenyl-S- mercaptotetrazol, 2,5 -dimercaptol ,3 ,4-thiadiazol, benzothiazol, cysteine, etc. However, these compounds are essentially only effective in a diffusion transfer processing system comprising hydroquinone and thiosulfate, and have never been used in combination with the hydroxylamine-cyclic imides (or amine compounds) system because they lower the transfer rate and exert no color toning effect. Taking the use of l-phenyl-S- mercaptotetrazol as a typical example, it not only inhibits diffusion transfer but it also gives a reversed image.

SUMMARY OF THE INVENTION It is therefore a principle object of this invention to provide a highly active viscous developing liquid whereby silver images of high density are obtained.

A second object of this invention is to provide a viscous developing liquid whereby positive images of high stability are obtained in a short processing period.

A third object of the present invention is to provide a viscous developing liquid whereby positive silver images of a blue-black tone are obtained.

A fourth object of this invention is to provide a viscous developing liquid whereby stable positive images free from contamination and discoloration after storage for long periods are obtained.

After extensive investigation, the inventors reached the present invention. In more detail, the present invention is characterized by the addition of at least one of the compounds represented by formulae (I), (II) or (III) to a viscous developing composition comprising a hydroxylamine-type developing agent, a sulfur-free nitrogen-containing silver halide solvent, a cellulose wherein R R and R are each a hydrogen atom, an alkyl or substituted alkyl group containing 1-4 carbon atoms, e. g., an hydroxyalkyl group, or a phenyl group, m is an integer of 2-4. and n is or an integer of 1-4 DETAILED DESCRIPTION OF THE INVENTION Typical examples of the groups represented by R R and R in the above formulae are a hydrogen atom, a methyl, ethyl, butyl, isopropyl, isobutyl, sec. butyl, tert.

butyl, hydroxymethyl, 2-hydroxyethyl, 3- hydroxypropyl, 4-hydroxybutyl, 3-hydroxyl methylpropyl, 1 -hydroxymethylpropyl,

l-hydroxymethyll -methylethyl or like group.

Specific examples of compounds represented by formulae (I) to (III) are as follows:

The amount of the compound or compounds represented by general formulae (I) to (III) is generally greater than 1 mg. per 100 g of the developing liquid, preferably from about 0.01 to about 0.1g per 100g of the developing liquid. Lesser or greater amounts can be used, of course, but if less 1 mg is used ofttimes the results achieved will not be very good, and in any case the difficulty of such exact low measurements does not make the use of smaller amounts desireable. Greater amounts do not substantially increase the results achieved, and hence are economically non-preferred.

The hydroxylamine type developing agent used in the present invention includes, for example, compounds such as the following: hydroxylamine, N-methyl hydroxylamine, N,N-dimethyl hydroxylamine, N,N- diethyl hydroxylamine, N-isopropyl hydroxylamine, N-methyl-N-isobutyl hydroxylamine, N,N-di-n-propyl hydroxylamine, N,N-di-(Z-methoxyethyl) hydroxylamine, N,N-di-(2-ethoxyethyl) hydroxylamine, N- methyl-N-2-dimethylaminoethyl-hydroxylamine, N-methyl-N-(N'-morpholino) methyl hydroxylamine, N,N-di-(2-methoxyethoxyethyl) hydroxylamine, N-ethyl-N-Z-ethoxyethyl hydroxylamine, N-allyl-N-2- ethoxyethylhydroxylamine, 3-(N-methyl) hydroxylaminopropionamide, N-methyl-N-2-(2- pyridyl )ethylhydroxylamine, N,N-bis- 2-( 2 pyridyl)ethyl]hydroxylamine, N-methyl-N-2-(4'- pyridyl)ethyl hydroxylamine, N,N-bis-[2-(4- pyridyl)ethyl]hydroxylamine, N-methyl-N-Z- ethylsulfonylethyl-hydroxylamine, N,N-bis-( 2- ethylsulfonylethyl)hydroxylamine, bis-Z-(methylhydroxylamino) ethylsulfone, N-hydroxythiomorpholine dioxide, etc. These compounds can be employed either singly or as combinations of two or more thereof. One skilled in the art will be aware of other hydroxylamine developing agents as this term is understood in the art, and the hydroxylamine type developing agents are not to be limited to those disclosed above.

Usually from about 0.5 to about 35 percent more preferably from about 2 to about 15 percent by weight of the hydroxylamine-type developing agent, based on the weight of developing composition, will be present in the viscous developing agent. At excessively lesser amounts insufficient developing agent may be present unless critical care is taken during development, and

hence one will generally use an amount within the ethyl amine, triethanol amine, monoethanol amine, ethylene diamine, aminoethyl ethanolamine and the like. These compounds can be used either singly or as mixtures of two or more thereof.

As a general rule, from about I to about 40 percent, preferably from about 5 to about 20 percent, by weight of the silver halide solvent is used based on the weight of the developing composition. Significantly lesser amounts should be avoided to insure a complete solublizing effect, while much greater amounts will seldom ever be required.

The cellulose derivative thickener used in the present invention includes, for example, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc., and such compounds may be used either alone or as mixtures of two or more thereof. These and equivalent materials serve their art recognized purpose in the present invention, and other equivalent cellulose derivative thickenees may be used, e.g., modified forms of the above materials.

For the viscous developing liquid to be uniformly I spread, it desirably has a viscosity within the range of from about 1,000 to about 200,000 centipoise. Therefore, the amount of the thickener added is preferably determined so as to impart a viscosity in the abovedefined range.

The alkali agent used in this invention includes, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide etc. The alkali agent should be added in an amount sufficient to provide the developing liquid with a pH above about 13.5 Although more exotic materials as are known in the art may be used to perform this pH adjusting function, the alkali metal hydroxides serve this purpose excellently, and are most preferred.

The developing liquid used in this invention may contain, if desired, standard ancillary additives as are used in this art, e.g., fogging inhibitors such as potassium bromide, 6-nitrobenzo-imidazol etc., antioxidants such as sodium sulfite, potassium metabisulfite, sodium benzene sulfinate, ascorbic acid, dihydroxy-benzene, phenol, etc.

In order to easily strip the negative material from the positive material after exposure and development, the developing liquid may be further include zinc or a zinc compound such as zinc chloride, zinc oxide, zinc hydroxide, zinc sulfate, zinc carbonate, etc. Of course, any stripping material as is known to the art for use in diffusion transfer elements may be used, but the zinc compounds are very effective when used in an amount of from about 7 X 10 to about 0.3 moles, preferably from 7 X 10' to 0.15 moles, calculated as metallic zinc, per 100g of developing solution.

It has already been disclosed in U.S. Pat. No. 3,565,619 to use the compound corresponding to general formula (I) in a diffusion transfer process. According to that U.S. Patent, a benzene or naphthalene type compound having both an hydroxyl group and an amino group attached orthoor parato each other is used as a developing agent, processing at higher temperatures being possible by the use of the compound of general formula (I). However, where a hydroquinone type compound is employed as a developing agent there unavoidably occurs, as previously stated, fouling and discoloration of the processed positive layer after storage for a long period of time, and a good color cannot be obtained.

According to the present invention, however, a greatly improved diffusion transfer processing system is provided which is not accompanied by any fouling or discoloration problems as are often encountered in conventional processes using a hydroquinonethiosulfate salt, and it is possible to achieve a greatly improved rate or speed of transfer as compared to conventional processes using hydroxylamine-cyclic imide compounds (or amine compouns).

It now becomes possible to conduct development in a short period and to obtain a silver image of high density. Moreover, a silver image of a fine blue-black tone can be obtained. These advantages can be attributed only to the surprising function of the compounds of general formulae (l)-(Ill), which not only give an adequate color toning or modifying effect but which also increase the transfer speed to a great extent. Neither of these functions or effects is disclosed in the foregoing United States Patent, and therefore, the results attained by this invention are quite unexpected.

There has also been proposed a positive material prepared by coating a support with an emulsion in which physical developing nuclei are dispersed, usually in a gelatin binder or in colloidal silica. However, since this of type positive material has inferior physical strength it has usually been necessary to use some aftertreatment for the positive material on which the image was formed. Such an after-treatment was also applied to prevent fouling or discoloration of the positive material.

By using the developing liquid of the present invention, it is now unnecessary to carry out after-treatment such as neutralization of the developed positive material or stabilization of the silver halide solvent. This is because a positive material of this invention is substantially free from fouling or discoloration. In this connection, the characteristic features of the developing liquid of this invention can be emphasized when used in combination by with a positive material containing physical developing nuclei or a cellulose acetate base due to the inherent high physical strength of such a material which completely eliminates the necessity of the aftertreatment.

The present invention will now be illustrated in more detail by the following non-limitative examples:

EXAMPLE 1 A highly sensitive momochromatic photo film comprising 3,3-diethyl-9-methylthia-carboxylamine bromide in a highly-sensitive (gold-and sulfur sensitized) gelatin-silver iodobromide emulsion (5 molar percent silver iodide) containing 8.5g of silver and 40g of gelatin per kilogram of emulsion on a triacetate cellulose film support was subjected to exposure through a light wedge. A positive material to be used in combination therewith was prepared as follow:

A cellulose acetate film (SO/L thick) had laminated thereto a high quality paper sheet (g/m and then a polyethylene layer was coated on the back of the cellulose acetate sheet to form a layer with a thickness of 40;].. The resultant sheet was immersed at 45C for 2 minutes in a solution of the following composition whereby the surface of the cellulose acetate film was hydrolyzed:

Water 400 g Ethanol 500 g Ethylene glycol g Sodium hydroxide I00 g The surface of the resultant sheet was further coated with a 6 percent by weight solution in methanol of nickel chloride (hexahydrate), dried, immersed in a 0.5 percent by weight aqueous solution of sodium sulfide for-one minute, water-rinsed and dried. A sufficient number of negative and positive elements were obtained to permit the runs in Table I to be completed.

Viscous developing liquids having compositions A-E were prepared by mixing the ingredient shown in Table 1 under a nitrogen atmosphere. Developing liquids A, B, C and E are given for comparison purposes.

*Manufactured by Hercules Co. Ltd.

The emulsion layer of a negative material as described and the image-receiving layer of a positive material as described were then placed together while spreading each viscous developing liquid therebetween until a thickness of about 90p was obtained. The positive layer was then stripped off after developing processing for 20 seconds and 40 seconds. The quality of the print thus obtained is given in Table 2. The reflection density shown in the table was measured by the use of a Type-P densitometer manufactured by Fuji Photo Film Co., Ltd.

tone having sufficient image density within a shorter processing time (refer to Table 2, Developing liquids B and D).

It can also be seen that compound l used in this example is not desirable as a color toning agent in a conventional diffusion-transfer system using hydroquinone-thiosulfate salt (refer to Table 2, Developing liquid E where a brown color tone was achieved, as opposed to the describable blue-black color tone).

EXAMPLES 2-4 The procedure of Example 1 was followed except for using a viscous developing liquid having the composition shown in Table 3.

TABLE 3 Example Compounds contained 2 3 4 Water 100 100 100 Natrosol hydroxyethyl cellulose (high viscosity") l0 l0 Carboxymethyl cellulose (low viscosity)** [5 15 N,N-di-(Z-methoxyethyl} I hydroxylamine 10 l0 l0 Uracil 30 30 Compound 2 0.1 Compound 5 0.1 Compound 7 0.01 Zinc chloride 3 3 3 Sodium hydroxide 25 25 25 *"*Manufacturcd by Hercules Co, Ltd.

Sets of the emulsion layer of the negative material and the image-receiving layer of the positive material, both as heretofore described, were combined while spreading therebetween each viscous developing liquid illustrated in Table 3. 20 seconds after spreading the viscous developing liquid therebetween, both materials were stripped from each other. The quality of the resultant print is given in Table 4.

TABLE 2 Developing liquid used Photographic performance A B C D E Color tone of image Blue- Yellow Brown Blue- Brown black black Reflection density at the portion of maximum density 20 seconds development 1.70 1.00 0.50 1.65 1.7 seconds development 1.85 1.65 1.12 1.80 1.8 After leaving the print at room temperature for a month degree of fouling at Reddish Reddish white portions of the print orange None None None orange degree of browning at Yellowy Yellowy image portions of the print brown None None None brown As will be seen from Table 2, a diffusion transfer pro- TABLE 4 cess using a hydroquinone-thiosulfate system will con vert a silver image into one of blue-black tone only Example Nu when a conventional color toning agent is used (refer 6O Photographic Performances 2 3 to Table Developmg. hquld but Such Cannot be Color tone of the image Blue- Blue- 7 Blueachieved in the processing system of the present mvenblack l k mack tion where the developed print can be stored for a long Reflection density of the time because some phenomena decreases the amount portion of maximum density L69 L80 172 of material transferred (refer to Table 2, Developing liquid C) unless the system of the present invention is used. That is, according to the present invention it is now possible to obtain an image of a blue-black color As will be clear from the results of Table 4, the viscous developing liquid of the present invention can convert a silver image into a true blue-black tone, and remarkably increases the speed of transfer.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

1. A viscous diffusion transfer process silver halide developing liquid containing at least one hydroxylamine type developing agent, at least one sulfer-free nitrogen-containing silver halide solvent, at least one cellulose derivative thickening agent and at least one alkali agent, which developing liquid contains at least one compound represented by one of the following formulae (I), (II) and (III):

wherein R R and R are each a hydrogen atom, alkyl group or a substituted alkyl group containing from 1 to 4 carbon atoms, or a phenyl group, m is an integer of from 2 to 4, and n is O or an integer of from 1-4.

2. The developing liquid of claim 1 where the compound has formula (I).

3. The developing liquid of claim 1 where the compound has formula (II).

4. The developing liquid of claim 1 where the compound has formula (III).

5. The developing liquid of claim 1 where the at least one compound of formulae (1), (II) or (III) is present in an amount greater than 1 mg per 100g of the developing liquid.

6. The developing liquid of claim 5 where the hydroxylamine type developing agent is selected from the group hydroxylamine, N-methyl hydroxylamine, N,N- dimethyl hydroxylamine, N,N-diethyl hydroxylamine, N-isopropyl hydroxylamine, N-methyl-N-isobutyl hydroxylamine, N,N-di-n-propyl hydroxylamine, N,N-di- 2-methoxyethyl) hydroxylamine, N,N-di-(2- ethoxyethyl) hydroxylamine, N-methyl-N-2- dimethylaminoethyl hydroxylamine, N-methyl-N-(N- morpholino) methyl hydroxylamine, N-N-di-(2- methoxyethoxyethyl)-hydroxylamine, N-ethyl-N-2- ethoxyethyl hydroxylamine, N-allyl-N-2-ethoxyethylhydroxylamine, 3-(N-methyl)hydroxylaminopropionamide, N-methyl-N-2-( 2 '-pyridyl )ethylhydroxylamine, N,N-bis-[2-(2'-pyridyl)ethyllhydroxylamine, N- methyl-N-2-(4'-pyridyl)ethyl hydroxylamine, N,N-bis- [2-( 4'-pyridyl )ethyl ]hydroxylamine, N-methyl-N-2- ethylsulfonylethyl-hydroxylamine, N,N-bis-(Z-ethylsulfonyl)hydroxylamine, bis-2-(methylhydroxylamine)-ethylsulfone, N-hydroxythiomorpholine dioxide, and mixtures thereof.

7. The developing liquid of claim 6 where the sulfurfree nitrogen containing silver halide solvent is a cyclic amide compound or an amine.

8. The developing liquid of claim 7 where the sulferfree nitrogen containing silver halide solvent is selected from the group consisting of cyanuric acid, barbituric acid, uracil, 4-methyl uracil, urazol, hydantoin, succinimide, ethyl amine, triethanol amine, monoethanol amine, ethylene diamine, aminoethyl ethanolamine, and mixtures thereof.

9. The developing liquid of claim 7 where the cellu lose derivative thickener is selected from the group consisting of methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and mixtures thereof.

10. The developing liquid of claim 9 where the alkali agent is an alkali metal hydroxide.

11. The developing liquidv of claim 5 wherein the amount is from about 0.01 to about lg per g of the developing liquid.

12. Thedeveloping liquid of claim 6 wherein the at least one hydroxylamine type developing agent is present in an amount of from about 0.5 to about 35 percent by weight of the developing composition.

13. The developing liquid of claim 7 wherein the amount of the sulfur-free nitrogen containing silver halide solvent present is about 1 to about 40 percent by weight of the developing composition.

14. The developing liquid of claim 9 wherein the cellulose derivative thickener is present in an amount sufficient to provide a viscosity to the developing liquid of from about 1,000 to about 200,000 centipoise.

15. The developing liquid of claim 1 where the developing liquid is at a pH of above about 13.5.

16. The developing liquid of claim 1 where the substituted alkyl group is hydroxyalkyl.

17. In a process for forming an image comprising the steps of:

a. exposing a negative material;

b. contacting the negative material with a, positive image receiving layer;

0. developing an image in the positive receiving material using a viscous developing liquid for a diffusion transfer process;

d. stripping the negative from the developed positive;

the improvement wherein the viscous silver halide developing liquid comprises at least one hydroxylamine type developing agent, at least one sulferfree nitrogen-containing silver halide solvent, at least one cellulose derivative thickening agent and at least one alkali agent, which developing liquid contains at least one'compound represented by one of the following formulae (I), (II) and (III):

wherein R R and R are each a hydrogen atom, an alkyl group or a substituted alkyl group containing from 1 to 4 carbon atoms, or a phenyl group, m is an 20. The process of claim 17 where the compound has formula (I).

21. The process of claim 17 where the compound has formula (II).

22. The process of claim 17 where the compound has formula (III).

23. The process of claim 17 where the sulfur-free nitrogen-containing silver halide solvent is a cyclic imide.

24. The process of claim 17 where the sulfur-free nitrogen containing silver halide solvent is selected from the group consisting of cyanuric acid, barbituric acid, uracil, 4-methyl uracil, urazol, hydantoin, succinimide, ethyl amine, triethanol amine, monoethanol amine, ethylene diamine, amino-ethyl ethanolamine, and mixtures thereof.

25. The process of claim 17 wherein said viscous silver halide developing liquid consists essentially of said at least one hydroxylamine type developing agent, said at least one sulfur-free nitrogen-containing silver halide solvent, said at least one cellulose derivative thickening agent, said at least one alkali agent and said at least one compound represented by one of the formulae (I), (II) and (III).

26. The developing liquid of claim 1 which further comprises zinc.

27. The developing liquid of claim 1 which further comprises a zinc compound.

28. The developing liquid of claim 27 wherein said zinc compound is selected from the group consisting of zinc chloride, zinc oxide, zinc hydroxide, zinc sulfate and zinc carbonate.

29. The developing liquid of claim 28 wherein the zinc compound is present in an amount of from aabout 7 X 10' to about 0.3 moles, calculated as metallic zinc, per g of developing solution.

30. The process of claim 17 where the developing liquid further comprises zinc.

31. The process of claim 17 where the developing liquid further comprises a zinc compound.

32. The process of claim 31 where the Zinc compound is selected from the group consisting of zinc chloride, zinc oxide, zinc hydroxide, zinc sulfate and zinc carbonate.

33. The process of claim 32 where the zinc compound is present in an amount of from about 7 X 10' to about 0.3 moles, calculated as metallic zinc, per 100 g of developing solution.

l l= =l=

Claims

2. The developing liquid of claim 1 where the compound has formula (I).
3. The developing liquid of claim 1 where the compound has formula (II).
4. The developing liquid of claim 1 where the compound has formula (III).
5. The developing liquid of claim 1 where the at least one compound of formulae (I), (II) or (III) is present in an amount greater than 1 mg per 100g of the developing liquid.
6. The developing liquid of claim 5 where the hydroxylamine type developing agent is selected from the group hydroxylamine, N-methyl hydroxylamine, N,N-dimethyl hydroxylamine, N,N-diethyl hydroxylamine, N-isopropyl hydroxylamine, N-methyl-N-isobutyl hydroxylamine, N,N-di-n-propyl hydroxylamine, N,N-di-(2-methoxyethyl) hydroxylamine, N,N-di-(2-ethoxyethyl) hydroxylamine, N-methyl-N-2-dimethylaminoethyl hydroxylamine, N-methyl-N-(N''-morpholino) methyl hydroxylamine, N-N-di-(2-methoxyethoxyethyl)-hydroxylamine, N-ethyl-N-2-ethoxyethyl hydroxylamine, N-allyl-N-2-ethoxyethylhydroxylamine, 3-(N-methyl)hydroxylaminopropionamide, N-methyl-N-2-(2''-pyridyl)ethylhydroxylamine, N,N-bis-(2-(2''-pyridyl)ethyl) hydroxylamine, N-methyl-N-2-(4''-pyridyl)ethyl hydroxylamine, N,N-bis-(2-(4''-pyridyl)ethyl)hydroxylamine, N-methyl-N-2-ethylsulfonylethyl-hydroxylamine, N,N-bis-(2-ethyl-sulfonyl)hydroxylamine, bis-2-(methylhydroxylamine)-ethylsulfone, N-hydroxythiomorpholine dioxide, and mixtures thereof.
7. The developing liquid of claim 6 where the sulfur-free nitrogen containing silver halide solvent is a cyclic amide compound or an amine.
8. The developing liquid of claim 7 where the sulfer-free nitrogen containing silver halide solvent is selected from the group consisting of cyanuric acid, barbituric acid, uracil, 4-methyl uracil, urazol, hydantoin, succinimide, ethyl amine, triethanol amine, monoethanol amine, ethylene diamine, aminoethyl ethanolamine, and mixtures thereof.
9. The developing liquid of claim 7 where the cellulose derivative thickener is selected from the group consisting of methyl cellulose, hydroxyethyl cellulose, carBoxymethyl cellulose, and mixtures thereof.
10. The developing liquid of claim 9 where the alkali agent is an alkali metal hydroxide.
11. The developing liquid of claim 5 wherein the amount is from about 0.01 to about 1g per 100g of the developing liquid.
12. The developing liquid of claim 6 wherein the at least one hydroxylamine type developing agent is present in an amount of from about 0.5 to about 35 percent by weight of the developing composition.
13. The developing liquid of claim 7 wherein the amount of the sulfur-free nitrogen containing silver halide solvent present is about 1 to about 40 percent by weight of the developing composition.
14. The developing liquid of claim 9 wherein the cellulose derivative thickener is present in an amount sufficient to provide a viscosity to the developing liquid of from about 1,000 to about 200,000 centipoise.
15. The developing liquid of claim 1 where the developing liquid is at a pH of above about 13.5.
16. The developing liquid of claim 1 where the substituted alkyl group is hydroxyalkyl.
17. In a process for forming an image comprising the steps of: a. exposing a negative material; b. contacting the negative material with a positive image receiving layer; c. developing an image in the positive receiving material using a viscous developing liquid for a diffusion transfer process; d. stripping the negative from the developed positive; the improvement wherein the viscous silver halide developing liquid comprises at least one hydroxylamine type developing agent, at least one sulfer-free nitrogen-containing silver halide solvent, at least one cellulose derivative thickening agent and at least one alkali agent, which developing liquid contains at least one compound represented by one of the following formulae (I), (II) and (III):
18. The developing liquid of claim 1 wherein said sulfur-free nitrogen-containing silver halide solvent is a cyclic imide.
19. The developing liquid of claim 1 consisting essentially of at least one hydroxylamine type developing agent, at least one sulfur-free nitrogen-containing silver halide solvent, at least one cellulose derivative thickening agent, at least one alkali agent and at least one compound represented by one of formula (I), (II) and (III).
20. The process of claim 17 where the compound has formula (I).
21. The process of claim 17 where the compound has formula (II).
22. The process of claim 17 where the compound has formula (III).
23. The process of claim 17 where the sulfur-free nitrogen-containing silver halide solvent is a cyclic imide.
24. The process of claim 17 where the sulfur-free nitrogen containing silver halide solvent is selected from the group consisting of cyanuric acid, barbituric acid, uracil, 4-methyl uracil, urazol, hydantoin, succinimide, ethyl amine, triethanol amine, monoethanol amine, ethylene diamine, amino-ethyl ethanolamine, and mixtures thereof.
25. The process of claim 17 wherein said viscous silver halide developing liquid consists essentially of said at least one hydroxylamine type developing agent, said at least one sulfur-free nitrogen-containing silver halide solvent, said at least one cellulose derivative thickening agent, said at least one alkali agent and said at least one compound represented by one of the formulae (I), (II) and (III).
26. The developing liquid of claim 1 which further comprises zinc.
27. The developing liquid of claim 1 which further comprises a zinc compound.
28. The developing liquid of claim 27 wherein said zinc compound is selected from the group consisting of zinc chloride, zinc oxide, zInc hydroxide, zinc sulfate and zinc carbonate.
29. The developing liquid of claim 28 wherein the zinc compound is present in an amount of from aabout 7 X 10 4 to about 0.3 moles, calculated as metallic zinc, per 100 g of developing solution.
30. The process of claim 17 where the developing liquid further comprises zinc.
31. The process of claim 17 where the developing liquid further comprises a zinc compound.
32. The process of claim 31 where the zinc compound is selected from the group consisting of zinc chloride, zinc oxide, zinc hydroxide, zinc sulfate and zinc carbonate.
33. The process of claim 32 where the zinc compound is present in an amount of from about 7 X 10 4 to about 0.3 moles, calculated as metallic zinc, per 100 g of developing solution.