US3232759A

US3232759A - Diffusion transfer process employing tone modifiers

Info

Publication number: US3232759A
Application number: US223532A
Authority: US
Inventors: Richard L White; Edwin B Wyand; Hugh G Mcguckin
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1962-09-13
Filing date: 1962-09-13
Publication date: 1966-02-01
Anticipated expiration: 1983-02-01
Also published as: DE1173798B; GB1052446A

Description

United States Patent 3,232,759 DIFFUSIONTRANSFER PROCESS EIVLPLOYING TONE MODIFIERS- Richard-L; White, Edwin B. Wyand, and Hugh G. McGuckin, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey N0 Drawing; Filed Sept-13, 1962,Ser. No. 223,532 14 Claims. (Cl. 9629)' This invention relates to.the production of positive photographic images by the methodgenerally known as the ditfusiontransfer process, more particularly, a process for improving thetone of the images obtained thereby.

In the diffusion transfer process alight-sensitive silver halide containing emulsion is exposed to lightand a negative image formed in' the photographic emulsion by developing. A silver solvent is used (generally in the developer) to cause diffusion of the unexposed silver salts onto. a receiving sheet held inface contact with the negative. The receiving sheet contains development nuclei which cause the diffused silver salts to form positive silver or silver salt images 'on the receiving sheet.

A problem encountered in the diffusion transferprocess has been that of producing a neutral positive image since the positive image which'isoften produced is of a brownish or other non-acceptable color. One solution to this-problem has-been disclosed in US. Patent No. 3,004,850, issued to Dickinson et al., October 17, 1961.

It has now been found'that a group of compounds can be used either singularly or in combination in small amounts and will produce a shift in the positive image tone toward a neutral color.

One object of this invention is to provide a process for obtaining an improved tone of the positive image obtained in the diffusion transfer process. Anotherv object is to obtain prints by the diffusion transfer process having satisfactory colors. Another object is to obtain the satisfactory neutral color in prints with a shorttransfer time. An additional object is to provide a group-- of compounds which can be used either singularly or in combination with an amine-type developer for improving positive image tone.

The above objects are attained by using at least one compound having the general formula:

wherein R1' andR represent identical alkyl groups such as Methyl, Ethyl, Or propyl,

or identical hydroxyalkyl groups such as:

2-hydroxyethyl, Or 2-hydroxy-1-propyl,

or, taken together, represent a saturated ring of five or six atoms such as:

Morpholinyl, Or piperidyl,

or, if R represents Hydrogen, Or methyl,

R represents hydroxyalkyl groups such as:

Z-hydroxyethyl, LI-dimethy'l-Z-hydroxyethyl,

1,1-(dihydroxymethyl)-ethyl, tris-(hydroxyniethyD-methyl, Or glucosyl;

111 represents a small integer;

n represents an integer between one and" six or a fraction representing a mixture of compounds in which n is between one and six, and

Z represents:

Hydrogen,

Hydrochloride, Cyanamide, as the isothiuronium salt, Formaldehyde, as a mercaptal, 7 Or a metal forming a complex, for instance-- Silver, Zinc, Or Zirconium,

with an amine-type developer inthe diffusion transfer process.

isbetween .01 and 10:0 g. per liter in the developingsolution. It will be clear that the developer containing the tone modifier can be'applied to the photographic emulsion using the usual means as well' as by incorporating it in a pod and squeezing ;it over the surfaoeof the exposed emulsion. It mayalso be used in conjunction with the web processing'method in which the exposed silver halide emulsion" layer'containing' a'latent photocolloid processing element or web. This processing ele ment contains dispersed silver'precipitat'ing agent, and at least at the'time of contact with'the' exposed emulsion layer, suflicient processing solution to develop the exposed silver-halide and to remove substantially all of the undeveloped silver halide. For example, a web'process'ing positive image which comprises exposinga photographic silver halide emulsion layer to an object or image, de veloping a negative image in the exposed layer, and during or after development, transferring silver halide-by diifusion from the unexposed areas of the emulsion layer to a non-light-sensitive image receiving layer containing a silver preci itating agent such as development nuclei or a substance capable of forming development nuclei with dissolved silver halide or a precipitant for silver salts by double decomposition and in effective contact with the emulsion layer, the transfer being effected in the presence of a silver halide'solvent and at least one compound of one of the above general formulas.-

In a preferred embodiment, the silver or zinc salt of the abovecompounds can be used. For intsance, diethylaminoethaneth-iol HCl can be added to silver nitrate to form the silver salt and added as the silver salt.

By in effective contact we means that dissolved silver salts can diffuse from the emulsion layer to the nonlight-sensitive layer. There may be anintermediate'layer present between the two aforesaid layers which does not hinder the silver salt diffusion, and the two layers may or may not be coated on the same support. 7 7

Alkaline solution is used to eifect development of the exposed layer and the developing agent may be present in either the emulsion layer or in the alkaline solution or both. A mixture of developing agents may be used, if desired.

The concentration of the above-tone modifier' graphic imageis contacted with a hydrophilieorg'a'nic The silver halide solvent may be present in the developing solution or the receiving layer and is preferably sodium thiosulfate.

It is preferable to employ an antifoggant to prevent the formation of fog in the exposed emulsion layer and this may be present in either the emulsion layer or in the alkaline solution used to elfect development. Any of the well known nitrogen-containing organic antifoggants may be used, or inorganic, such as potassium bromide, which are very suitable.

A suitable known light-insensitive image receiving layer for use in the present invention comprises a gelatin layer containing a substance constituting development nuclei (such as colloidal silver or silver sulfide) or a substance forming development nuclei with dissolved silver salts (such as zinc sulfide), and also containing at least one of the compounds of this inveniton.

Such a layer may be coated on a paper or film support and contacted in the presence of a silver halide solvent with an exposed and developing emulsion layer which may be coated on a separate support, or may be coated on the same support as the emulsion layer. In the latter, it is preferable to coat the non-light-sensitive layer on a paper support and then to overcoat this layer with a comparatively unhardened emulsion layer. After exposure, development and formation of a direct positive image in the nonlight-sensitive layer, the exposed and developed unhardened emulsion layer is removed, for example by washing in warm water. The following examples are intended to illustrate our invention but not to limit it in any way:

Example 1 A coating was made on a white, opaque, cellulose acetate support. It was comprised of a 30 mg./ft. nucleated gelatin layer coated over a 1000 mg/ft. gelatin pad. The nuclei were lead sulfide precipitated in 1.5% gelatin.

The web coating was soaked for three minutes in a developer consisting of:

Grams 2,2-iminodiethanol-SO addition product, 13% S by weight 200.0 4,4-dimethyll -phenyl-3 -pyrazolidone l .0 Hydroquinone 1 1.0 Sodium thiosulfate 8.0 Potassium iodide 0.4 Diet'hylaminoethanethiol HCl 0.05 3-mercapto-1,2,4-triazole 0.05

Water to make 1 liter.

Example 2 A dry processing web was used which consists of a hydrophilic layer comprising, in each square foot, 2 g. gelatin, 8 mg. lead sulfide nuclei, a hardener, and a coat- .ing aid coated on polyethylene terephthalate film support. The dry web was soaked for 3 minutes in a developer consisting of:

Grams 2,2-iminodiethanol-SO addition pro duct, 13

S0 by weight 200.0 4-methyl-1-phenyl-3-pyrazolidone 2.0 Hydroquinone 9.0 Sodium thiosulfate, crystalline 75.0 Diethylaminoethanethiol HCl 0.5 Water to make 1 liter.

Sodium hydroxide to pH 10.00.

The web was removed from the developer and was wound on a spool together with an exposed roll of photographic film having thereon a silver halide emulsion in such a manner that the emulsions of the two strips were in contact. After 10 minutes, the two strips were pulled apart, revealing a neutral tone positive image in the web having a partially fixed negative. After additional fixing, a useable negative obtained, although of low contrast. The addition of diethylaminoethanethiol HCl in this process, by itself produce good neutral tones and density in the web image. Best results were obtained when the negative film was exposed at the recommended film index of 1250.

Example 3 A processing web was prepared and soaked as in EX- ample 2 except that the amount of diethylaminoethanethiol HCl was 0.75 g. per liter, also, the Web-soak time was increased to 5 minutes instead of 3 minutes. Two films were exposed at their recommended exposure indexes of 80 and 200, respectively, and processed by means of the web. After additional fixing, a useable negative of adequate contrast was obtained with both films. The addition of diethylaminoethanethiol I-ICl, as in Example 2, produced good neutral tones and density in the positive web images.

-Example 4 A processing web was prepared by coating on each square foot of a cellulose acetate support, 2 g. gelatin, 8 mg. lead sulfide nuclei, and 9 mg. diethylaminoethanethiol l-ICl, together with a hardener and a coating aid.

The web was soaked for 5 minutes in 5 ccs. of the same developer solution used in Example 2 but with the diethylaminoethanethiol HCl omitted. The web was then rolled in contact with an exposed 35mm. roll of highspeed negative gelatino silver bromoiodide photographic film using a wind-up type processor. After 10 minutes, the film and web were separated.

Neutral tone positive images were obtained in the web after processing.

' Example 5 A receiving sheet was prepared by coating, on each square foot of a white pigmented cellulose acetate sup port, 1 g. gelatin, 0.45 mg. nickel sulfide nuclei, 260 mg. hypo, 21 mg. 5-diethylaminoethyl-iso-thiuronium chloride HCl, and 0.22 mg. 2 mercapto 5 phenyl 1,3,4- oxadiazole, together with a hardener and a coating aid The receiving sheetand a sheet of exposed, very highspeed negative gelatino silver bromoiodide photographic film were both soaked for 15 seconds in a developer consisting of:

Grams 2,2iminodiethanol-SO addition product, 13

so by weight 200.0 Hydroquinone 40.0 4-methyl-l-phenyl-3-pyrazolidone 0.5

After soaking, the two sheets were brought in contact by means of wringer rollers. After 1 /2 minutes processing time, the strips were pulled apart to reveal a neutral tone positive image in the receiver.

Example 6 A similar experimental processing web was prepared: as used in Example 4 by coating on a white pigmented cellulose acetate support 1 g. gelatin, 500 mg. hypo, and 10 mg. diethylarninoethanethiol HCl per squ are foot, to-- gether with a hardener anda coating aid.

The receiver and an exposed sheet of very high-speed.

negative gelatino silver bromoiodide photographic film were each soaked for 15 seconds in a developer consisting Grams 2,2'-iminodiethanol-SO addition product, 13%

S0 by weight 100.0

Sodium sulfite .0.

Z-methylhydroquinone 3 0.0 4-methyl-1-phenyl-3-pyrazolidone 0.2 Potassium brornide 10.0

Water tomake 1 liter. Sodium hydroxide to pH 11.1.

Processing was carried out as described in ExampleS. Neutral tones resulted in the positive image of the receiver.

Example 7 A receiver wasipreparedby coatinga layer on 'white pigmented cellulose acetate support which was comprised of:

Mgjft. Gelatin 360.0- Sodium.sulfite, anhydrous 25.0 Sodium thio'sulfate, pentahydrate 50.0-

(Ethylenedinitrilo) tetraacetic acid, tetrasodium salt 100.0 (Ethylenedinitrilo) tetraacetic acid, trisodiurnsalt- 200.0v Nickel sulfide nuclei 0.18 1..- methyl 1,2,3,6 tetrahydro 1,3,5 triazine- 4-thiol 4.0 3,8 dithiadecane 1,10 .bis(-N methylpiperidinium pts.) 10.0

A hardener anda coating, aid were also presentinthecoating solution. Addition-a1 coatings weremade'containing 0.75, 1.5, 3.0,:an d 4.5 mg. diethylaminoethanethiol HCl per square foot. The composition of the negative may be summarized asfollowsz.

Mg./ft. Support: Cellulose acetate filrnwith antihalation pelloid backing.

Sheets of the negative materials were exposed, soaked in tap water for 1 second, and immediately rolled in contact with the sheets of the receiver. After 2 minutes, each pair of sheets was separated.

In the absence of diethylaminoethanethiol HCl, a weak, yellowbrown image was. formed in the receiver. The addition of the diethylaminoethanethiol HCl to the extent of 1.5 mg. per square foot shifted the tone to neutral and increased the image density considerably. At the level of 4.5 mg. per square foot, the density was slightly higher. However, the level of3.0 mg. per square foot was preferred for this particular combination.

Example 8 A processing web as described in Example 2 was soaked for 3 minutes in a basic processing solution comprising:

Gr m Pe ite Th w t e w ee s and rs lsd in mt st with n eis s st Strip of i hee e e l t p e i o il r sr i Ph o a i fi mer 5 in te processing period, the strips' were separated, The web contained only a faint yellow image.

250 mg. of diethylarninoethanethiol HCl was added per liter of processing solution. A heavy deposit of silver was found in the Web indicating the greater eflioiency of 6: transfer and toning action over the control. When a similar run was made with the addition of 10 ml. of 2- methylarninoethanol per liter, the tone was more'brown than above indicating that the toning ,action of the diethylaminoethanethiol HCl is more efficient in the presence of an amine.

Example 9 A processing web consisting of a cellulose acetate support coated,'in each-square f0Ot,With a 500 mg. gelatin layer and a 50 mg. gelatin layer containing 0.18 mg. of nickel sulfide nuclei, both layers moderately hardened, was soaked for-10 seconds at 90, F. in a processing solution consisting of Methyladinoethanol-SO addition product, 20% S0 by weight ml 160 Hydroqu-inone g 20 1-phenyl-3-pyrazolidorie g 0.5 Sodium thiosulfate, pentahydrate g 40 -3 dimethylaminopropylisothiuroniumchloride HCl Water to makel liter.

The web was removed from the processing solution,

rolled in contact with a fine-grain silver chlorobromide negative material and allowed to process for 30 seconds in a water bath whose temperature was-"F. The strips were then separated, revealing blue-black positive image in the web and a developed negative which required an additional fixing treatment. The omission of the 3-dimethylaminopropylisothiuroniumchloride .HCl from the processing solution caused theaformation ofan orangecolored positive in the Web. Thefollowing structural,

formula for-3-dirnethylaminopropylisothiuroniumchloride H01:

(3-climethylaminopropylisothluroni um chloride HCl) indicates the reaction which occurs in analkaline solution. The cyanamide group splits-off from the isothiuronium salt leaving .the active agent, 3-dimethylarnino propanethiol.

Example 10 The processing web of Example 2 was soaked for 3 minutes at room temperature in a processing solution con-v sisting of;

3-dirnethy-larninopropylisothiuronium chloride HCl 0.5 Wa er to m ke 1 r,

The --web-was removed from; the processing solution and rolled in contact with an exposed strip offine-grain. Silver re q id ne t e m t i l n. s wha m nner that the two emulsions were in contagt; After 10 minutes of't ransfer at room temperature the strips were pulled pa t r e l a n a t n p t v i age n the W th and a completely fixed negative,

E mple 11 p o es in s ti nwas p epa e co t n ng a 10wp yt sr f ky m noa k n h Z-hyd QXyJA-dimetm ylethylaminooligoethylenesulfidee1,69

Clix HQ 2 NH( 2 2S) 1120B 1,1-dimethyl 2 hydroxyethylaminooligoethylenesulfide-1.69 0.75 Water to make 1 liter.

The web of Example 2 was soaked in the solution for 3 minutes, removed and rolled in contact with an exposed strip of a fine-grain silver bromoiodide negative material in such a manner that the two emulsions were in contact. After ten minutes of transfer at room temperature, the strips were pulled apart, revealing a blue-black positive image in the web and a completely fixed negative. When the toning agent was omitted from the processing solution, a brown image was formed in the web.

For the oligomeric compounds of the type used in Example 11, higher degrees of polymerization were also eflective, as in the case of 1,l-dimethyl-2-hydroxyethyl aminooligoethylene sulfide-2.9.

C H; HOCH2( 3NH(CH GHzS)z.e

Example 12 An experimental processing web like that of Example 2 was soaked for ten seconds at 90 F. in a processing solution consisting of:

Methylaminoethanol-SO addition product, 20% S by weight ml 160 Hydroquinone grams 20 1-pheny1-3-pyrazolidone do 0.5 Sodium thiosulfate, pentahydrate do 40 l,1-dimethyl-2-hydroxyethylaminooligoethylene sulfide-2.9 grams 0.2

Water to make 1 liter.

The web was removed from the processing solution, rolled in contact with the negative material of Example 9, and allowed to process for 30 seconds in a water bath whose temperature was 90 F. The strips were then separated, revealing a blue-black positive image of good density in the web and a developed negative which required an additional fixing treatment. Orange tones were obtained in the positive image in the web when the toner was omitted from the processing solution.

Example 13 A Web like that of Example 9 was soaked for ten seconds at 90 F. in a processing solution consisting of:

Methylaminoethanol ml 50 Sodium sulfite, anhydrous grams 20 Hydroquinone do 20 4,4-dimethyl-1-phenyl-3-pyrazolidone do 2 Sodium thiosulfate, pentahydrate do 30 Sulfuric acid to pH of 10.0. 1,1 dimet-hyl 2 hydroxyethylam-inooligoethylene sulfide-2.9 gr-am 0.5

Water to make 1 liter.

The web was removed from the processing solution, rolled in contact with a moderate-speed silver bromoiodide negative material, and allowed to process for 60 seconds in a water bath whose temperature was 90 F. The strips were then separated revealing a blue-black positive image in the web and a developed negative which required an additional fixing treatment.

A combination of the toner 1,1-dimethyl-2-hydroxyethylaminooligoethylene sulfide 2.9 and diethylaminoethanethiol HCl was found to be particularly efifective in the photographic system of Example 7.

8 Example 14 The negative of Example 7 was exposed and soaked in tap water for six seconds. It was then rolled in contact with a receiver which was prepared by coating a layer on white-pigmented cellulose acetate support which was comprised of:

Mg./ft. Gelatin 360.0 Sodium sulfite, anhydrous 25.0 Sodium thiosulfate, pentahydrate 50.0

Ethylenediaminetetraacetic acid, tetrasodium salt 100.0 Ethylenediaminetetraacetic acid,trisodium salt 200.01

Nickel sulfide nuclei 0.14 Diethylaminoethanethiol HCl 19.2; Sulfuric acid to pH of 10.0. l,l-dimethyl-2-hydroxyethylaminooligoethylene sul tide-2.9 "gram" 0.5

together with a hardener and a coating aid. After two minutes, the two sheets were separated. The receiver contained a high-density, neutral-toned positive image.

Other compounds similar to 2-hyd-roxy-1,1-dimethylethylaminooligoethylenesulfide-1.69 and 1,1-dimethyl-2- hydroxyethylaminooligoethylenesulfide-2.9 were found to be effective in combination with diethylaminoethanethiol HCl in the system of Example 14.

2-hydroxyethylaminooligoethylene sulfide-1 N-methylglucaminooligoethylene sulfide-5 .6

5 HO oH2(ononnommomcmsmrt N (Z-aminoethyl)-2-hydroxyethylaminooligoethylene sulfide-1.75

CH GHZ V ornonzs qfin HzNCHzCHz Morpholinoethanethiol v (\S EW-CHzCHzSH 2 morpholinoethylisothiuronium, chloride hydrochloride (ll-.HCl

Example 15 Strips of a negative like that described in Example 7 were exposed, soaked for six seconds in water or a solution comprising 0.75 gram of diethylaminoethanethio] HCl per liter, and then placed in contact with a receiver 9 like that of Example 14 except that the toners were omitted. The receiver images had the following appearance:

Solution Transfer time Receiver image appearance Water 2 min Orange. Diethylnminoethane- 2 min Weak brown.

thiol H01.

D 3 min Neutral, high density.

Example -1 6 A negative whose composition may be summarizedas follows: Support: Cellulose acetate film with antihalation pelloid .was exposed and soaked ,for six seconds in a solution containing approximately 500 .mg. diethylarninoethanethiol .and 200 mg. 1,1edimethyl-Lhydroxymethy-laminooligeethylene sulfide-2.9 perliter. Both compoundswerepresent in the solution as silver complex salts, formed by combining one mole of silver nitrate with two moles of the organic compound. The formation of a tightlybound complex was indicated by the disappearance ofthe characteristic odor of each compound. After soaking, the negative was rolled in contact with a receiver like that of Example 14 but from which the toners had been omitted. After three minutes, the two sheets were separated, revealing a neutral-toned positive image in the receiver.

Example I 7 The experiment of the preceding example was repeated with the water for soaking the negative containing 0.5 gram of 2-dimethylaminoethylmercapto zinc chloride hydrochloride and 2.0 grams of 2-morpholinoethylisothiuronium chloride hydrochloride per liter. A neutral-toned positive image was obtained.

Example 18 Processing web A was prepared which comprised, per square foot, 2000 mg. gelatin, nickel sulfide nuclei, 12 mg. diethylaminoethanethiol, a hardener and a coating aid, coated on a polyethylene terephthalate support. In a second web, B, the 12 mg. of diethylaminoethanethiol had previously been combined with 6 mg. of silver nitrate. The webs were soaked for periods of time ranging from 1 1 to 12 minutes at 70 F. in a processing solution comprising:

Grams 2,2'-iminodiethanOl-SO addition product, 12.8%

S0 by weight 200 4,4-dimethyl-1-phenyl-3-pyrazolidone 2 Hydroquinone Sodium thiosulfate, pentahydrate 100 Sodium hydroxide to pH 10.5. Water to make 1 liter.

and placed in contact with exposed strips of a fine-grain gelatino silver bromoiodide negative for ten minutes.

The negatives for both webs showed only a slight increase in speed and contrast as the web soak time was in creased. The positive images in Web A showed a progressive lowering of contrast, as represented by a lengthening of the toe and a falling off of the shoulder, as the soak time was increased. The shape and position of the positive curve in Web B was not influenced by the length of 10 the soak period. It was evident that the diethylaminoethanethiol was slowly washed out of Web A during the soaking period, while, as the silver salt in Web B, the loss of the compound was eliminated or at least greatly reduced.

Example 19 Processing webs like those of Example 18 above were prepared in which Web C contained no toning agent and Web D contained 4 mg. of diethylaminoethanethiol per square footcomplexed with 2 mg. of silver nitrate. Samples of the two webs were incubated for one week at 100 F. and percent relative humidity. The incubated and non-incubated Webs were soaked for 4 minutes at 70 F. in a solutioncomprised of:

Grams Methylaminoethanol-SO addition product, 19% S0 by weight Dimezone 2 Hydroquinone 10 Sodium thiosulfate, pentahydrate 100 Ethanol 100 Water to make 1 liter.

and placed in contact withexposed strips of a fine-grain gelatino silver bromoiodide negative material for ten minutes. Incubation of the processing webs caused the positive image curves ,to be shifted in adirectionrepresent- Processing Web A is prepared. as described in Example 18 except that in the second web, B, the 12 mg. of diethylaminoethanethiol is combined with 6 mg. of Zinc nitrate. The web-s are soaked for periods of time ranging from 1 to 12 minutes at 70 F. in the processing solutiondescribed in Example 18, and placed in contact with exposed strips of a fine-grain gelatino silver brornoiodide negative for ten minutes.

The negatives for both webs show only a slight increase in speed and contrast as the web soak time was increased. The positive images in Web A show a progressive lowering of contrast as represented by a lengthening .of the toe and a falling off of the shoulder, as the soak time is increased. The shape and position ofthe ositive curve in Web B is not influenced by the length of the soak period. It is evident that the diethylaminoethanethiol is slowly washed out of Web A during the soaking period, while, as the Zinc salt in Web B, the loss of the compound is eliminated or least greatly reduced.

Example 21 aminoethanet-hio-l the same amount of transfer can take place in 15 or 20 seconds. The effect was observed a. diffusion transfer system containing a toning agent com: bination disclosed and claimed in the Tregillus et al. US. Patent No. 3,017,270 as extended by the US, patent ap= plication Ser. No. 141,036, filed September 27, 1961 and now abandoned, by A. A. Rasch, P. B. Gilman, and J. E. Jones.

A fine-grain gelatino silver bromoiodide negative film was exposed and then dipped for six seconds at 70 F. in a solution comprising:

Grams 2,2'-iminodiethanol-SO addition product, 12.8%

80 by weight 160.0 Methylaminoethanol-SO addition product, 19%

S by weight 20.0 1-phenyl-3-pyrazolidone 1.0 Hydroquinone 12.0 Sodium thiosulfate, pentahydrate 60.0 Triton X-200 (surfactant) 0.5 Sodium hydroxide to pH 10.5.

Water to make 1 liter.

As Run A, the negative was immediately placed in contact for 20 seconds at 70 F. with a receiver consisting of a white-pigmented at 70 F. with a receiver consisting of coated, per sq. ft., 1000 mg. gelatin, 0.3 mg. nickel sulfide nuclei, a hardener, and a coating aid.

Run A was repeated with the following changes:

Run B.2.0 grams per liter of 3.8-dithiadecane-Ll0- bis(N-methylpiperidiniurn-p-toluene sulfonate) were added to the processing solution.

Run C.0.1 gram of l-methyl-1,2,3,6-tetrahydro- 1,3,5-triazine-4-thiol were added to one liter of the processing solution.

Run D.The additions of Runs B and C were combined.

Run E.The negative was dipped in the solution of Run D and placed in contact with a receiver containing, in addition, a complex formed by combining 4 mg. of diethylaminoethanethiol and 2 mg. of silver nitrate.

The positive images in the receivers of the various runs were found to possess the following characteristics:

Subsequently, the receiver and processing solution were modified slightly and rebalanced so that the image tone was substantially neutral and the maximum density was on the order of 1.6.

Polymeric sulfides described as useful in this invention are described in pending US. patent application 165,931, filed January 12, 1962 and now abandoned, in the names of Johnson and Reynolds.

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

We claim:

1. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing developing nuclei, transfer being effected in contiguity with sufficient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, a toning compound, said compound being different from the silver halide solvent, having the general formula:

wherein R and R are selected from the class consisting from the class consisting of hydrogen, iminocarbamoyl,

hydroxymethyl, silver, zinc and Zirconium.

2. The process of claim 1 wherein the toning compound is incorporated in the developer solution.

3. The process of claim 1 wherein the toning compound is incorporated in the image receiving layer.

4. A process for preparing a photographic image which comprises developing an exposed photographic sil ver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufficient silver halide solvent, other than diethylatninoethanethiol HCl, to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, diethylaminoethanethiol HCl.

5. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by dilfusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufiicient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, 2-hydroxyethylaminooligoethylene sulfide.

6. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufficient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, 2-hydroxy-1,1-dimethylethylaminooligoethylene sulfide.

7. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sulficient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, morpholinoethanethiol.

8. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufficient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, 1-1-(dihydroxymethyl)- ethylaminooligoethylene sulfide.

9. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with Sllfil cient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an

alkanolamine and, in addition, tris-hydroxymethylmethylaminooligoethylene sulfide.

10. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufiicient silver halide solvent to remove substantially all un developed silver halide from the emulsion layer, an alkanolarnine and, in addition, bis(2-hydroxy-l-propyl) aminooligoethylene sulfide.

11. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity With sufllcient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, N-methylglucaminooligoethylene sulfide.

12. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufficient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, N-(2-aminoethyl)-2- hydroxyethylaminooligoethylene sulfide.

13. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer With a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufficient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alk-anolamine and, in addition, the silver salt of diethylaminoethanethiol HCl.

14. A process for preparing a photographic image which comprises developing an exposed photographic silver halide emulsion layer with a silver halide developing agent and transferring the silver halide by diffusion from the undeveloped areas of the emulsion layer to a supported image receiving layer containing development nuclei, the transfer being effected in contiguity with sufficient silver halide solvent to remove substantially all undeveloped silver halide from the emulsion layer, an alkanolamine and, in addition, the zinc salt of diethylaminoethanethiol HCl.

References Cited by the Examiner UNITED STATES PATENTS 2,698,245 12/1954 Land 96-29 2,875,048 2/1959 Haist et al. 96-61 2,984,565 5/1961 Morse 96-29 3,017,270 1/1962 Tregillus 96--29 FOREIGN PATENTS 594,237 Belgium. 1,243,430 9/1960 France.

OTHER REFERENCES Photographic Science and Engineering, 5, July-August 1961, pp. 198-203.

NORMAN G. TORCHIN, Primary Examiner.

Claims

1. A PROCESS FOR PREPARING A PHOTOGRAPHIC IMAGE WHICH COMPRISES DEVELOPING AN EXPOSED PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER WITH A SILVER HALIDE DEVELOPING AGENT AND TRANSFERRING THE SILVER HALIDE BY DIFFUSION FROM THE UNDEVELOPED AREAS OF THE EMULSION LAYER TO A SUPPORTED IMAGE RECEIVING LAYER CONTAININ DEELOPING NUCLEI, TRANSFER BEING EFFECTED IN CONTIGUITY WITH SUFFICIENT SILVER HALIDE SOLVENT TO REMOVE SUBSTANTIALLY ALL UNDEVELOPED SILVER HALIDE FROM THE EMULSION LAYER, AN ALKANOLAMINE AND IN ADDITION, A TONING COMPOUND, SAID COMPOUND BEING DIFFERENT FROM THE SILVER HALIDE SOLVENT, HAVING THE GENERAL FORMULA: