JPS6239734B2 - - Google Patents

Description

Claim 1: A support comprising a silver halide emulsion in a layer carried by the support and an image dye-providing substance in a layer carried on the same side of the support as said silver halide emulsion; The image dye-providing material has at least one diffusion control group selected from the group consisting of a silver halide developing group, a color coupling group, a sulfonamidophenol group, and a thiazolidine group, and also has the formula: (wherein each R is the same or different and is an alkyl group, and each X is the same or different and is hydrogen or an alkyl group) sexual element. 2. A photographic light-sensitive element as defined in claim 2, wherein each R is an alkyl group and each X is an alkyl group. 3 The image dye-providing substance has the formula: [wherein each Y is a diffusion control substituent containing a diffusion control group D, and X' is hydrogen, alkyl or -(CH ₂ -X ² -D) _o (where X ² is a divalent bonding group, And n is 0 or 1,
at least one of n is 1). 4. A photographic light-sensitive element as defined in claim 3, wherein said image dye-providing material is a magenta dye developer and said diffusion control group D is a silver halide developing group. 5 The diffusion control substituent Y is a group -A-D
A photographic light-sensitive element as defined in claim 3, wherein A is a covalent or divalent bond group and each D is a hydroquinolyl group. 6. A photographic light-sensitive element as defined in claim 3, wherein said diffusion control group D is a color coupling group. 7. A photographic light-sensitive element as defined in claim 3, wherein said diffusion control group D is a sulfonamidophenol group. 8. A photographic light-sensitive element as defined in claim 3, wherein said diffusion control group D is a thiazolidine group. 9. Said light-sensitive element comprises a red-sensitive silver halide emulsion in combination with a cyan dye developer, a green-sensitive silver halide emulsion in combination with said magenta dye developer, and a blue-sensitive silver halide emulsion in combination with a yellow dye developer. A photographic light-sensitive element as defined in claim 4 comprising a silver emulsion. 10 A photographic light-sensitive element as defined in claim 3, wherein X' is aralkyl. 11 The dye developer is: A photographic light-sensitive element as defined in claim 4. 12 The dye developer is: A photographic light-sensitive element as defined in claim 4. 13 The dye developer is: A photographic light-sensitive element as defined in claim 4. 14 The dye developer is: A photographic light-sensitive element as defined in claim 4. 15 The dye developer is: A photographic light-sensitive element as defined in claim 4. 16 The dye developer is: A photographic light-sensitive element as defined in claim 4. 17 The dye developer is: A photographic light-sensitive element as defined in claim 4. 18 The dye developer is: A photographic light-sensitive element as defined in claim 4. 19 The dye developer is: A photographic light-sensitive element as defined in claim 4. 20 The dye developer is: A photographic light-sensitive element as defined in claim 4. Description This invention relates to photography, particularly magenta dyes for use in providing diffusion transfer color images, and photographic products and methods using such magenta image dyes. Multicolor images formed according to the principles of subtractive color photography use yellow, magenta and cyan image dyes.
Yellow dye ideally transmits only green and red light and absorbs only blue light. This is sometimes referred to as "minus blue." Similarly, magenta (“minus green”)
A green) dye ideally absorbs only green light and transmits only blue and red light, and a cyan ("minus red") dye ideally absorbs only red light, Transmits only blue and green light. Unfortunately, the dyes available for use in subtractive color photography are not "ideal" dyes and tend to absorb some of the light that ideally should be transmitted. This extra absorption impairs the final image's reproduction of one or two colors present in the object. This problem can be explained by considering the reproduction of blue light. It consists of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, each silver halide emulsion layer having a yellow image dye-providing substance, a magenta image-providing substance and a cyan image dye-providing substance therein. The multicolor photosensitive element having the combination of materials is exposed to a sufficient amount of blue light so that the blue sensitive layer is fully exposed. Only the blue sensitive silver halide layer is exposed; the green sensitive and red sensitive silver halide emulsion layers remain unexposed. When a photosensitive element thus exposed is processed with a diffusion transfer technique, the yellow image dye-providing material remains in the developed photosensitive element (negative parts), while the magenta and cyan image dyes are transferred to the image-receiving layer (positive parts). transcribed. Since magenta and cyan dyes are "minus green" and "minus led" respectively, the combination of magenta and cyan dyes appears blue, i.e. they transmit blue light to the viewer and absorb green and red, thus The blue record of the object is reproduced. From this explanation, if either the magenta or cyan image dye also absorbs blue light, it produces a "blue image"
It is easily seen that the purity and quality of the product will be compromised. In the world of practical color photography, this undesirable absorption, sometimes referred to as "tail" absorption, is no exception. Magenta image dyes typically exhibit significant absorption in the blue region. The present invention is directed to providing magenta image dyes that exhibit reduced blue absorption, ie increased blue transmission. A primary object of the present invention is to provide a magenta image dye-providing material that produces diffusion transfer color images exhibiting more desirable color properties. Another object of the present invention is to provide a magenta dye developer that transmits blue light at a high rate. Another object of the present invention is to provide a magenta image dye-providing material useful in dye release diffusion transfer processes, such as radox dye release silver catalyzed dye release, and to provide a magenta image dye providing material that exhibits high blue transmission. Our purpose is to provide image dyes. Yet another object of the present invention is to provide a magenta image dye-providing material that transmits a high percentage of blue light and exhibits good green light absorption. Yet another object of the present invention is to provide diffusion transfer products and methods using such magenta image dye-providing materials. Other objects of the invention will be apparent in part and in part hereafter. For a further understanding of the nature and purpose of the invention, reference should be made to the following detailed description. In particular, the present invention provides a method for forming a desired image by processing an exposed photosensitive silver halide material with a processing composition distributed between two sheet-like elements, one of which contains the photosensitive material. About how to get photos. 2 so that the treatment composition does not contact or wet the external surfaces of the stacked elements.
It is applied within and between sheets of sheet-like elements to provide a film unit or film packet which is thus confined and dry on the outside. The treatment composition may be viscous or non-viscous and is preferably distributed from single-use rupturable containers; such pressure rupturable containers are often referred to as "pots." The final image, which may be monochrome or polychromatic, is formed in an image-receiving layer contained in one of the sheet-like elements. As is well known in diffusion transfer photography, the image dye-providing substances that can be used in such processes are (1) initially soluble or diffusible in the processing composition, but as an effect of development; or (2) an imagewise distribution of products that are initially insoluble or non-diffusible in the processing composition but can selectively diffuse as an effect of development. It can be characterized as either providing These image dye-providing materials may be complete dyes or dye intermediates, such as color couplers. The necessary differences in mobility or solubility can be obtained by chemical effects such as redox reactions, coupling reactions or splitting reactions. According to the present invention, A magenta image dye containing a chromophore system of the formula: where each R is an alkyl group and each X is hydrogen or an alkyl group (including substituted alkyl) has highly desirable spectral properties that include high blue transmission. It was discovered that it shows. Each R and each X may be the same or different. In a preferred embodiment,
Each R is an alkyl group of 1 to 4 carbons, preferably each R is a methyl group. In a particularly useful and preferred embodiment, each R and each X is an alkyl group,
In some cases, at least one of X is substituted alkyl such as aralkyl. An image dye-providing material capable of providing an image dye containing a chromophore system of formula A may be provided by the inclusion of a diffusion control substituent Y containing a diffusion control group D. One such group of image dye-providing substances can be represented by formula B: [In the formula, each Y is a substituent containing a diffusion control group D, and X' is hydrogen, alkyl (including substituted alkyl), or -(CH ₂ -X ² -D) _o (in the formula, X ² is 2
a valence-binding group, preferably an alkylene group having 1 to 4 carbon atoms, and each n is 0 or 1, provided that at least one of n is 1]. Image dye-providing materials falling under formula B are suitable for use in diffusion transfer processes using image dye-providing materials that are either initially diffusible or initially non-diffusible as a function of the particular diffusion control group D. There is. Examples of diffusion control groups D include sulfonamidophenol groups, color coupling groups, which release diffusible dyes or dye intermediates by oxidation followed by fission or ring closure;
Mention may be made of the hydroquinolyl group and the thiazolidine group, the splitting of which is catalyzed by silver.
The diffusion transfer control group D may be bonded to a covalent bond or a divalent bonding group, such as an alkylene group having 1 to 4 carbon atoms, to form a substituent Y.
Dyes in which X' is not hydrogen are preferred and exhibit a shift in absorption maximum and narrow absorption band towards intermediate green colors compared to dyes in which X' is hydrogen. moreover,
Dyes in which X' is not hydrogen have a small color shift in alkali. Compared to dyes with a -COO ^- group instead of -SO ₃ ^- , the dyes of the invention resist ring closure and undergo decolorization in an active environment. If the image dye-providing material is initially diffusive, a suitable ballast group, such as a long chain alkyl group, may be attached to the diffusion control group. One resonance form of the chromophore system represented by formula A can be shown as follows: In a preferred embodiment of the invention, the diffusion control group is a hydroquinolyl group and the resulting dye developer is an initially diffusible image dye-providing material.
Howard G. Rogers
A photosensitive element containing a dye developer and a silver halide emulsion is exposed to light and a processing composition is applied thereto, as disclosed in U.S. Pat. For example, it is applied in the dark by dipping, painting, spraying, pouring, etc. Before, during or after application of the processing composition, the exposed photosensitive element is applied onto a sheet-like support element which can be used as an image receiving element. In a preferred embodiment, the processing composition is applied to the exposed photosensitive element in a practically uniform layer such that the photosensitive element is in stacked relationship with the image-receiving layer. A processing composition disposed between the photosensitive element and the image-receiving layer penetrates the emulsion and initiates development of the latent image contained therein. The dye developer becomes immobile or precipitates in the exposed areas as a result of development of this latent image. This immobilization is
At least part of this depends on the solubility properties of the dye developer upon oxidation, particularly related to its solubility in alkaline solutions. Also, part of it may be due to the tanning effect of the oxidized developer on the emulsion, and part of it may be due to localized depletion of the alkali as a result of development. In the unexposed and partially exposed areas of the emulsion, the dye developer is unreacted, diffusive, and therefore free of unoxidized material that can diffuse into the processing composition as an effect of the point-to-point degree of exposure of the silver halide emulsion. Provides imagewise distribution of dye developer.
at least one of the imagewise distributions of this unoxidized dye developer.
The transferred image is substantially free of oxidative dye developer. The image-receiving layer receives deep diffusion of unoxidized dye developer from the developed emulsion without appreciably interfering with its imagewise distribution to provide a developed image reversal or positive color image. The receiving element may contain suitable adjuvants to mordantly or otherwise fix the diffused unoxidized dye developer. In the preferred embodiment of the '606 patent and certain commercial applications thereof, the desired positive image is revealed by separating the image-receiving layer from the photosensitive element at the end of a suitable invisibility period. Alternatively, as also disclosed in U.S. Pat. No. 2,983,606, the support for the image-receiving layer and the layer intermediate the other support and the image-receiving layer are transparent and the developed silver halide emulsion ( If a processing composition is applied between the image-receiving layer and the silver halide emulsion(s), the processing composition contains a substance effective for masking the silver halide emulsion(s), such as a white pigment. There is no need to separate the photosensitive element from the stack in contact with the photosensitive element following transfer imaging. As pointed out in the above-mentioned US Pat. No. 2,983,606, dye developers are compounds that contain both a dye chromophore system and also a silver halide developing group in the same molecule. "Silver halide developing group" means a group suitable for developing exposed silver halide. A preferred silver halide developing group is a hydroquinonyl group. Generally, developing groups include benzenoid developing groups, ie, aromatic developing groups that produce quinonoids or quinones when oxidized. Multicolor images can be obtained using dye developers in a diffusion transfer process by several techniques. One such technique designed to use integrated multilayer photosensitive elements to form multicolor transfer images using dye developers is described, for example, by Edwin H.; Edwin H.Land and Howard G. No. 3,345,163 issued Oct. 3, 1967 to Rodgers and U.S. Pat. No. 2,983,606, which disclose at least two selective The sensitized photosensitive layers are processed together with a single conventional image-receiving layer without separating them together. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, each of which emulsions being subjected to cyan dye development, e.g. It contains a combination of a magenta dye developer, a magenta dye developer, and a yellow dye developer. The dye developer can be used in the silver halide emulsion layer, for example in grain form, or it can be placed in a layer behind each suitable silver halide layer. Each set of dye developer combined with silver halide emulsion can be separated from another set by a suitable interlayer, such as a layer or stack of gelatin or polyvinyl alcohol. In some cases it may be desirable to incorporate a yellow filter before the green-sensitive emulsion, and such a yellow filter can be incorporated into the interlayer.
However, if desired, a separate yellow filter may be omitted by using a yellow dye developer having suitable spectral properties and present in a state capable of functioning as a yellow filter. A particularly useful product for obtaining multicolor dye developer layers is Edwin H. December 1968 against Rand
It is disclosed in US Pat. No. 3,415,644, issued on the 10th. This patent discloses a photographic product and method in which a photosensitive element and an image-receiving element are held in a fixed relationship prior to exposure and maintain this relationship as a laminate after processing and imaging. In these products, the final image is transparent (support) against a light-reflective, i.e. white, background.
Seen through the elements. Exposure to light is through this transparent element, and when the processing composition is applied, it provides a layer of light reflective material that provides a white background. Light-reflecting materials (in this patent, “opacifying agents”)
The pacifing agent] is preferably titanium dioxide, which also has an opacifying effect, i.e., is effective in masking the developed silver halide emulsion so that the transferred image is free from interference. It also serves to protect the light-sensitive silver halide emulsion from post-exposure fog due to light passing through the transparent layer when the exposed film unit is removed from the camera before imaging is complete. . Edwin H. U.S. Pat. No. 3,647,437, issued March 7, 1972 to Rand, relates to improvements in the product and method disclosed in U.S. Pat. The application of light absorbing materials to enable processing to be carried out under light conditions is disclosed. A light-absorbing material or auxiliary agent, preferably a PH-sensitive phthalein dye, is located and/or configured so as not to interfere with the exposure, and is present between the exposed silver halide emulsion and the transparent support during post-exposure processing. The emulsion is positioned so as to absorb light that could cause fog on the exposed emulsion. Furthermore, the light-absorbing material is positioned and/or configured after processing so as not to interfere with viewing the desired image a short time after the image is formed. In a preferred embodiment, a light-absorbing material, sometimes referred to as an optical filtering agent, is initially included in the treatment composition along with a light-reflecting material, such as titanium dioxide. The concentration of the light-absorbing material is selected to provide the light-transmitting opacity required to perform the particular method under the selected light conditions. In particularly useful embodiments, the light-absorbing dye is highly pigmented at the PH of the treatment composition, e.g., 13-14;
Substantially non-absorbing to visible light at lower PHs, eg, below 10-12. This PH reduction can be effected by an acid-reactive agent suitably arranged in the film unit, for example in a layer between the transparent support and the image-receiving layer. The dye developer is preferably chosen according to its ability to provide colors useful for practicing subtractive color photography, namely cyan, magenta and yellow. The dye developers used can be incorporated into each silver halide emulsion or, in a preferred embodiment, in a separate layer behind each silver halide emulsion. Such a dye developer layer may contain a film-forming natural or Applications can be made using coating solutions containing dye developers distributed in synthetic polymers. In accordance with the present invention, a magenta dye developer containing a chromophore system of formula A can be applied to a dye developer as defined by formula B, whose diffusion control group D is a silver halide developing group, such as a hydroquinolyl group. . In such image dye-providing materials, the diffusion control substituent Y can be represented by -A-D, where D is a hydroquinonyl group and A is a covalent or divalent group, such as alkylene. can. Such dye developers include the following dyes: Dyes 18 and 19 are Alain L., filed April 24, 1979 with Serial No. 32876. Alan L.Borror, Louis Cincotta
Cincotta), Edward M. Edward M. Mahoney and Mitsushiel H. Michael H.Feingold
is the subject of a pending application. Dye developers of the above type include, for example, dichlorosulfonefluorescein and, for example, the expression (wherein X, R and Y are as defined above and each R ² is the same and is hydrogen or a lower alkyl group). When R ² is alkyl, dealkylation of the resulting product regenerates the hydroquinone group. If only one hydroquinonyl group is desired in the dye developer, the dichloro starting material is first reacted to replace one chloro group with an anilino group, and then the hydroquinonyl-containing anilino group is reacted according to the above reaction. Introduce groups. Alternatively, aminoalkylhydroquinones can be reacted with sulfonyl chloride-substituted anilino-substituted sulfonefluorescenes to provide dye developers such as dyes 5 and 6 above. Compounds of formula D in which A is an alkylene group of 1 to 5 carbon atoms are defined by Blout, Green, Rogers, Simon and Woodward, February 22, 1966. U.S. Patent No.
It is disclosed in No. 3236893. Compounds within formula D in which A is a covalent bond are covered by U.S. Pat.
Disclosed in No. 3134811. Compounds in formula C where A is -SO ₂ - are labeled as green on November 16, 1965.
No. 3,218,312, issued in 1999. A is -S-alkylene ("alkylene"
Compounds within formula D containing 1 to 5 carbons), e.g. No. 3,009,958, issued November 21, 1961, and US Pat. No. 3,081,339, issued March 12, 1963, both issued to Green and Rosiers.
Disclosed in the issue. Compounds within formula D where A is -S- are described by Green and Rodiers in 1961.
It is disclosed in US Pat. No. 3,009,958, issued November 21st. Compounds within formula D where A is -O- are referred to as Green and Solodar.
Disclosed in U.S. Pat. No. 3,061,434, issued October 3, 1961. For convenience, the disclosures of these US patents are hereby incorporated by reference. When the anilino group(s) contains an amino or aminoalkyl substituent, the hydroquinonyl group can be isolated by reaction with a carboxylic acid-substituted hydroquinone, such as a cognate acid lactone or a cognate acid chloride, followed by blotting. It can be introduced by following the method disclosed in US Pat. Alternatively, can be reacted with one or both chlorines of dichlorosulfonefluorescene; compounds of this type are described in U.S. Pat. Disclosed in No. 3214469. Examples of the preparation of dye developers according to the invention are given below by way of illustration and without intending to be limiting. Example 1 Dichlorsulfone fluorescein 5.0g (0.012
mole) and 5.0 g of 2,6-dimethylaniline
(0.041 mol) were refluxed together in 50 ml of methanol for 0.5 h. Excess methanol was stripped off and the residue was triturated with diethyl ether.
Solidified. The solid was collected, washed well with diethyl ether, and then dried. Chromatography on Florsil (90/10 chloroform/methanol as solvent, by volume) as an orange powder; 3.0 g (44%) of monochloro intermediate was obtained. 25 ml of ethylene glycol was heated in an oil bath adjusted to 130° C., and nitrogen was bubbled in with stirring for 1 hour. To this hot deoxygenated ethylene glycol, the above intermediate
3.0g (5.2×10 ^-3 m) and 4.0 g (15.7 × 10 ^-3 m) of Add this solution to 130
The mixture was stirred at ℃ while slowly blowing nitrogen. Appropriate amounts were worked up periodically (TLC in methanol/chloroform, 15/85 parts by volume). After 4 hours, the hot reaction mixture was poured into 5% hydrochloric acid. The precipitate was collected, washed with water, and then dried. A small amount of monochloro intermediate was found to be present. This was removed by extraction with chloroform in a Soxhlet extractor. Thus purified dye 1
3.0g (81% yield) was obtained, This product showed a maximum absorption in methyl cellosolve at 534 nanometers, Epsilon 64000. Methanol/tetrahydrofuran (15/85 parts by volume)
Column chromatography using 534 nanometers in methyl cellosolve gave a purer sample of dye 1 showing an epsilon of 79,000 at 534 nanometers. Example 2 In a 250ml flask, add 30ml of dimethyl sulfoxide.
ml, dichlorsulfone fluorescein 6.0g
(0.0148 mol), 9.0g (0.0300mol) of and magnesium oxide
Add 6.0g. Argon was bubbled through the stirred mixture for several minutes, then the flask was placed in an oil bath set to 140°C. The reaction was performed using TLC (Q5F plate,
10/90 methanol/chloroform, by volume)
I tracked it. After 2.5 hours, the reaction appeared nearly complete. Sodium sulfanilate (10.0 g) was added and the reaction mixture was heated to 140°C for another 1 hour.
Holds time. After cooling to 90° C., 30 ml of water were added and the mixture was stirred and allowed to cool to solidify the dye mass. The solid was collected, washed well with water, dissolved in chloroform, and then dried over calcium sulfate. The chloroform was evaporated to obtain 15.0 g of crude dye. The crude dye was redissolved in chloroform and loaded into a Florisil column. The column was eluted with methanol/chloroform (15/85 parts by volume) and the column was washed to collect the dye. Evaporate the eluate and Obtained 8.0g (58%). A solution of 8.0 g (8.6 x 10 ^-3 mol) of this dye in 500 ml of chloroform was cooled in a dry ice-acetone bath, then boron trifluoride (21.1 g,
0.084 mol) was slowly added dropwise to this stirred solution. Once the addition of boron trifluoride is complete,
The mixture was allowed to come to room temperature and then stirred overnight. water 450
A solution of 50 ml of concentrated hydrochloric acid in ml was carefully added and the mixture was stirred and then refluxed for 1 hour. Filter the warm mixture, wash the solid thoroughly with water, then dry, dye 2: Obtained 6.0g (80%). Dye 2 showed a maximum absorption of Epsilon 104,000 at 548 nanometers in methyl cellosolve. Dimethoxy intermediate used in Example 2 above was manufactured as follows. Example 2-A Concentrated sulfuric acid 600g (362ml) and concentrated nitric acid (d.1.42)
100 g (71.5 ml) were combined together in three three-neck round bottom flasks and cooled to 0° C. in an ice-salt bath. To this was added dropwise 120 g (1 mol) of tolualdehyde with stirring and at a rate to maintain a temperature of about 5°C. After addition of the aldehyde, the solution was stirred at 0° C. for 1 hour and then dumped onto ice. Crude 4-methyl-3-nitrobenzaldehyde precipitated as a pale yellow solid, which was collected, washed with water, and then dried (mp 41-43°C). 18.0 g (0.1 mol) of 2,5-dimethoxyacetophenone and 16.5 g (0.1 mol) of 4-methyl-3-nitrobenzaldehyde
was dissolved in 75 ml of absolute ethanol with gentle heating on a steam bath. Gaseous hydrogen chloride was bubbled into this for several minutes with stirring. The still hot green solution was stoppered and left overnight at room temperature. Crystal 3-Nitro-
4-Methyl-2',5'-dimethoxychalcone and washed well with cold alcohol; yield 28g.
(86%). The substance recrystallized from toluene is 146-
It melted at 147°C. 30 g (0.046 mol) of this chalcone was placed on a Parr apparatus in ethanol at 40 lb/kg.
hydrogenated in square inches. After hydrogen suction stopped, the bottle was taken out and the precipitate was dissolved by heating. The crystals were filtered from the hot solution. When the liquid is cooled, crystallized as white crystals. This ketone 5.8g
(0.019 mol) was refluxed with 2.5 g (0.05 mol) of hydrazine hydrate in 25 ml of absolute ethanol for 1 hour. Slipping off ethanol and turning it into powder
4.0 g (0.071 mol) of KOH was added. This mixture was stirred and heated under nitrogen at 235° (oil bath temperature) for 45°C.
Heated for a minute. After cooling, the residue was stirred in water to dissolve the crystalline KOH and the oil was taken up in diethyl ether. After washing with water, the ether solution was dried on a dry light. The diethyl ether was evaporated to give an oil which solidified on standing. This solid was dissolved in 5 ml of hot toluene and 15 ml of boiling petroleum ether was added. This amine Upon cooling, a white powder (3.1 g, 57% yield;
mp65-66℃). This amine
10.0g (0.035 mol) of toluene containing 6g of 88% formic acid
It was refluxed in 150ml. Water was removed with a Dean-Stark trap; when there was no excess water (approximately 2 hours), the solution was allowed to cool slightly and further
Added 6g. The solution was refluxed again until free of water. TLC (50/50 diethyl ether/petroleum ether, by volume) until all starting material is removed.
and showed that a second compound was formed.
The solvent was evaporated under reduced pressure and the residual oil was dissolved in boiling ether. When cooled, formamide precipitated as a white powder (mp 107-108°C; 95% yield). Dissolve 4.5 g (0.0144 mol) of this formamide in 50 ml of tetrahydrofuran, _and
Treated with 6.6 g (0.087 mol) of DMS (boron-dimethyl sulfide). The solution was stirred at room temperature over the weekend, during which time a gelatinous precipitate formed. The reaction mixture was poured into 150 ml of water containing 10 ml of concentrated hydrochloric acid with stirring. After cooling, the mixture was made strongly basic by addition of solid sodium carbonate. The organic phase was taken up in diethyl ether and dried on Drylite. Evaporation of the solvent gave an oil which crystallized on cooling. The solid was triturated in petroleum ether and filtered; 4.0g (93% yield) of pure white powder, mp39-40℃
Obtained from. The following examples illustrate the preparation of sulfonyl chloride-substituted intermediates that can be used in the preparation of various dye developers within the scope of this invention. Example 3 Monochloro intermediate 6.0g (0.012mol) and 8.0 g (0.036 mol) of was heated in ethylene glycol overnight. The hot purple solution was poured into aqueous HCl to remove the solid. The solid was slurried in water and solid potassium hydroxide was added to form a solution. The solution was extracted twice with chloroform and the aqueous layer was isolated and acidified to approximately PH1 with concentrated hydrochloric acid. After heating to 90°C, salt was slowly added with stirring and the solid dye began to precipitate. Stir the temperature to 45
This was continued until the temperature dropped to -50°C, and the dye was removed. Refine it 4.0g of was obtained. 4.0 g (6 x 10 ^-3 moles) of this dye was slurried in 50 g thionyl chloride. 2.0 ml of dimethylformamide was added and the solution was stirred at room temperature for 1 hour. After pouring over ice while stirring,
The sulfonyl chloride was removed and washed well with water. After suctioning with a rubber dam, the moist material is dissolved in tetrahydrofuran, dried on a dry light and then evaporated, I got it. The sulfonyl chloride prepared in Example 3 can be reacted with a wide variety of amino-substituted hydroquinones to provide dye developers within the scope of this invention. That is, for example, the dye 5 contains this sulfonyl chloride. It can be produced by reacting with and then demethylating. A dye developer containing two such sulfonamide-linked hydroquinonyl groups can be used in place of both chlorines of dichlorosulfonefluorescene, e.g. can be obtained by reacting the resulting bis-sulfonyl chloride with two equivalents of the desired amino-substituted hydroquinone. The following example is presented to illustrate the use of the dye developer of the present invention in a diffusion transfer process. Example 4 A primed clear 4 mil polyethylene terephthalate film base was coated with a solution of Dye 2 and cellulose acetate hydrogen phthalate dissolved in a 50:50 volume mixture of acetone and methyl cellosolve to give approximately 24 mg/ft ² of Dye 2 and cellulose acetate hydrogen phthalate. A photosensitive element was made by forming a layer containing about 24 mg/ ^ft2 of phthalate. On top of this dye layer, a green-sensitive silver iodine bromide emulsion is applied.
A coverage of 44 mg/ft ² and gelatin 88 mg/ft ² was applied. A gelatin layer containing approximately 30 mg/ft ² of gelatin and 7.5 mg/ft ² of 4'-methylphenylhydroquinone was coated over this silver halide emulsion. The resulting photosensitive element was then exposed to a test exposure scale or step wedge on a sensitometer (2 meter-candle-seconds). In a dark place, approximately 100 g of a treatment composition containing (approximate concentrations)
A 0.0020-inch layer was formed between the exposed photosensitive element and the transparent image-receiving element in a stacked relationship: Potassium hydroxide (45% solution) 380 g Carboxymethyl hydroxyethyl cellulose
52g Titanium dioxide 2028g 6-Methyluracil 14.2g Bis-(β-aminoethyl)-sulfide
1g 5-Bromo-6-methyl-4-azabenzimidazole 1.5g Benzotriazole 27g Lithium nitrate 0.1g Colloidal silica (30% aqueous solution) 88g N-2-Hydroxyethyl-N,N',N'-Tris- Carboxymethyl-ethylenediamine
40g Lithium hydroxide 5g Polyethylene glycol (molecular weight 6000) 26g N-phenethyl-α-picolinium bromide (50% aqueous solution) 70g N-benzyl-α-picolinium bromide (50%
% aqueous solution) 121 g 6-benzylaminopurine 19 g Water 1757 g The resulting laminate was kept in the dark for 10 minutes (to avoid fogging of the silver halide emulsion developed by light passing through the transparent film base). ). When exposed to light, a well-defined positive magenta dye image (reflection density D _nax 1.70, D _nio 0.33) was deposited through the transparent base of the receiver element against the background of a white layer of titanium dioxide provided by the processing composition. Visible without separating elements. Inspection of the developed photosensitive element through the transparent film base of the photosensitive element showed a well defined negative silver image in the developed silver halide emulsion layer, and very little magenta dye developer remained. was left in the development zone, indicating effective use of the applied dye developer. The receiving element used in Example 4 was: 1 about 8 parts by weight of a partial butyl ester of polyethylene/maleic anhydride and about 1 part by weight of polyvinyl butyral to provide a polymeric acid layer having a coverage of about 2500 mg/ft ² A mixture of: 2 parts of hydroxypropyl cellulose (klucel J12HB Hercules, Inc., Wilmington, Delaware) to form a spacer layer having a coverage of about 500 mg/ft ²
and 3. (a) a mixture of about 2 parts polyvinyl alcohol and 1 part poly-4-vinylpyridine and hydroxyethyl cellulose to form an image-receiving layer having a coverage of about 300 mg/ft ² ; It consisted of 4 mil clear polyethylene terephthalate supported on a mixture of 1 part of the above graft copolymer of 4-vinylpyridine and vinylbenzyltrimethylammonium chloride (molar ratio 1:0.5:1). The figure is a graph of the percent visible light reflection versus wavelength in nanometers of a magenta monochrome reflective print produced in substantially the same manner as in the previous example, measured after three days of treatment using magnesium carbonate as a reference material. be. As mentioned above, the chromophore system according to the invention The magenta image dye-providing materials containing are not limited to dye developers, but include many other types of initially diffusive and initially non-diffusible image dye-providing materials. For example, Howard Gee. U.S. Patent No. 30, issued April 30, 1963 to Rosiers.
The initially diffusible coupling dyes useful in the diffusion transfer process disclosed in US Pat. It can be produced by substituting with. Examples of such coupling dyes include: can be mentioned. Although the dye is initially diffusible, color developers such as p-phenylenediamine or p-
-Couples with the oxidation product of aminophenol to form a less diffusible product, which becomes non-diffusive. When this coupling position is substituted with a substituent which renders the dye initially non-diffusible by various ballast groups and which cannot be substituted upon coupling, such a dye can be used to
For example, US Patent No. 6, issued January 6, 1966.
The principles disclosed in No. 3,227,550 can be used to provide diffusible dyes that cause coupling. An initially non-diffusible "redox dye-releasing method useful in the diffusion transfer process disclosed in U.S. Pat. No. 4,076,529 issued February 28, 1978 to Fleckenstein and Figueras" Examples of redox dye releasers include: can be mentioned. With this technology, for example, US Patent No. 25, 1977, issued to Koyama et al.
No. 4055428 and Freckenstein 1977
Other sulfonamide phenol or naphthol groups known in U.S. Pat. Can be used in place of amido-naphthol. U.S. Pat. No. 3,719,489 issued March 6, 1973 to Ciecuch, Luhowy, Meneghini and Rogers discloses that a diffusible image dye-providing material is initially non-diffusible. Discloses a diffusion transfer process in which images are formed by silver-catalyzed cleavage of the thiazolidine groups of the dye-providing material. Within the scope of the invention,
Examples of image dye-providing materials that can be used in the thiazolidine dye release system are: includes. Against Bloom and Rosiers
Another class of initially non-diffusible image dye-providing materials, disclosed in U.S. Pat. No. 3,433,939, issued May 13, 1969, liberates the diffusible dye upon oxidation and intramolecular ring closure. Examples of image dye-providing materials within the scope of this invention that can be used in the method of this patent are: It is. The initially non-diffusible image dye-providing materials exemplified above can be prepared by conventional methods, such as from a chromophore-containing group sulfonyl chloride (e.g., the sulfonyl chloride prepared in Example 3) and a suitable amino-substituted diffusion control group. , its composition is described in the said patent and reference may be made for a detailed description thereof, including photographic applications. Other image dye-providing materials that split with alkali with oxidation are those in which A is -O- or -S- and the hydroquinonyl group is a ballast group, e.g. to Anderson and Lum using a compound within formula D above containing
U.S. Patent No. 3725062 issued April 3, 1973
It can be provided in accordance with the disclosure in the issue. Although the ballast group in the above example is a long chain alkyl group, it will be appreciated that other ballast groups shown in the related cited patents may also be used. When using a non-diffusible image dye-providing material that liberates a diffusible image dye-providing material upon oxidation in an alkaline environment, the necessary oxidation is caused by the oxidation of the mobile developer used to develop the exposed silver halide emulsion. This can be done with oxidation products. A particularly effective developer for this purpose is 1-phenyl-4,4-dimethyl-3
- pyrazolidones; other suitable developers are disclosed in related cited patents. Example 5 A film unit was formed as follows: A negative element was made from a polyethylene terephthalate photographic film base on which the following layers were applied in sequence: 1 Cellulose acetate hydrogen phthalate 32 mg/
1932 mg/m of dye dispersed in ft ² (344.4 mg/m ² )
ft ² (344.4 mg/ft ² ) coverage of magenta dye developer layer; 2 silver 75 mg/ft ² (807.3 mg/ft ² ) and gelatin.
Green-sensitive gelatinoiodine silver bromide emulsion coated at a coverage of 88 mg/ft ² (947.2 mg/m ² ); 3 layer of gelatin 30 mg/ft ² (322.9 mg/m ² ). The receiving element consists of a transparent polyethylene terephthalate photographic film base having the following layers coated thereon in sequence: 1 about 2600 mg/ft ² (27986
about 9 parts of a partial butyl ester of polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral, applied at a coverage of 2 mg/m ² ) and containing UV-absorbing substances; 2 butyl acrylate, diacetone acrylamide, styrene and 60-30- of methacrylic acid
4-6 quaternary polymer approx. 450mg/ft ² (4843.8mg/
^m2 ) and contains about 7% polyvinyl alcohol.
3. 3 parts of a mixture of (a) 2 parts polyvinyl alcohol and 1 part poly-4-vinylpyridine applied at a coverage of about 300 mg/ft ² (3229.2 mg/m ² ); HEC/4VP/TMQ is composed of 4-vinylpyridine (4VP) and vinyl-benzyltrimethylammonium chloride (TMQ) grafted onto hydroxyethylcellulose (HEC).
A polymeric receptor of a graft copolymer composition having a ratio of 2.2/2.2/1. This film unit was treated with a treatment composition consisting of the following ingredients: Water 1757g Bis-(β-aminoethyl)-sulfide
1.04cc Titanium dioxide 2028g Potassium hydroxide (50% solution) 380.3g Carboxymethylhydroxyethyl cellulose
51.8g Benzotriazole 26.9g 6-Methyluracil 14.2g N-Hydroxyethyl-N,N',N'-Tris-carboxymethylethylenediamine 40.2g 6-Methyl-5-bromo-4-azabenzimidazole 1.34g 6-Benzyl Aminopurine 19.0g Lithium nitrate 4.72g Polyethylene glycol (molecular weight 6000) 26.1g Colloidal silica (50% aqueous dispersion) 88.5g N-benzyl-α-picolinium bromide (50
% solution) 121.3 g N-pheneethyl-α-picolinium bromide (50% solution) 70.0 g This film unit was exposed with a sensitometer to a test exposure scale (2 meters-
candle-seconds) and then passed through a pair of rollers with a gap of about 0.0020 inches. The unit was kept in the dark for approximately 10 minutes. The film units were held together and the maximum and minimum reflection densities were measured. Example 6 Dye developer layer of negative element is dye 18 28.0mg/ft ²
The procedure of Example 5 was repeated except that it was made from (301.4 mg/m ² ) and cellulose acetate hydrogen phthalate 28.0 mg/ft ² (301.4 mg/m ² ). EXAMPLE 7 The method of Example 6 was repeated except that the gelatin layer of the negative element also contained 7.5 mg/ft ² (80.7 mg/m ^{2 )} of methylphenylhydroquinone. EXAMPLE 8 The gelatin layer of the negative element also contained 7.5 mg/ft 2 of methylphenylhydroquinone. Example 9 The method of Example 7 was repeated except that the dye developer layer of the negative element contained Dye ² (80.7 mg/ft ^{2 )} .
and cellulose acetate hydrogen phthalate 24.6
The procedure of Example 5 was repeated except that it was formed from mg/ft ² . Example 10 The procedure of Example 9 was repeated except that the gelatin layer of the negative element also contained 7.5 mg/ft ² (80.7 mg/m ² ) of 4'-methylphenylhydroquinone. The monochrome magenta transfer images obtained in Examples 5-10 showed the following reflection density for green light: D _nax D _nioExample 5 2.09 0.69 Example 6 2.03 0.64 Example 7 2.20 0.25 Example 8 2.00 0.22 Example 9 2.22 0.57 Example 10 2.33 0.30 Example 11 As cyan and yellow dye developer and a multicolor photosensitive element by applying the following layers to a gelatin-primed 4 mil opaque polyethylene terephthalate film base using Dye 18 as the magenta dye developer: 1 about 630 mg/m ² of dye, about 391 mg gelatin/ ^m2 , N
-n-dodecylaminopurine approx. 280mg/ ^m2 and 4'-methylphenylhydroquinone approx. 88mg/m2
A layer of cyan dye developer dispersed in gelatin applied at a coverage of m ² ; 2 about 1054 mg/m ² silver and about 6324 mg gelatin/m ²
red-sensitive gelatinoiodine silver bromide emulsion coated at a coverage of 3; 60-30-4-6 copolymer of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid coated at a coverage of about 1076 mg/m ² 4 layers of a 95:5 mixture of dye and polyacrylamide; 4 about 648 mg/m ² of dye and about 324 mg/m ² of gelatin
a layer of magenta dye developer dispersed in gelatin, coated at a coverage of 5; green-sensitive gelatin powder dispersed in gelatin, coated at a coverage of about 749 mg/m ² of silver and about 330 mg/m ² of gelatin; Layer of plain silver bromide emulsion; 6 Contains the copolymer used above in layer 3 and polyacrylamide in a ratio of 91:9, approximately 1816 mg/m ²
7. Approximately 659 mg/m ² of dye, approximately 318 mg/m ² of gelatin and approximately 108 mg/m of N-n-dodecylaminopurine.
A layer of yellow dye developer dispersed in gelatin, applied at a coverage of m ² ; 8 blue-sensitive gelatinoiodine-silver bromide, applied at a coverage of about 990 mg silver/m ² and about 495 mg gelatin/m ² Emulsion layer; 9. A layer of gelatin coated at a coverage of approximately 320 mg gelatin/m ² . A transparent 4 mil polyethylene terephthalate film base was applied in the following layers to form the image receiving element: 1 Partial butyl ester of polyethylene/maleic anhydride copolymer at a coverage of approximately 2500 mg/ft ² as the polymeric acid layer. and polyvinyl butyral in a ratio of about 9:1; 2 with a 60-30-4-6 copolymer of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid at a coverage of about 450 mg/ ^ft2 ; 3. 4-vinylpyridine and vinylbenzyltrimethylammonium chloride on polyvinylalcohol, poly-4-vinylpyridine and hydroxycellulose at a coverage of about 300 mg/ ^ft2 ; 2 of the graft copolymer (2.2:1:2.2 ratio) with
Image receiving layer containing a 1:1 mixture. On this image-receiving layer, about 100 mg/ft ² of a 70:30 mixture of Pluronic F-127 polyoxyethylene polyoxypropylene block copolymer and polyvinyl alcohol was applied as a decolorizing layer. [Such a "decolorizing" layer is
Edwin H., serial number 33001, filed April 24, 1979. land. Leon D. is the subject of a pending application by Leon D. Cerankowski and Neil Mattuci]. This photosensitive element is exposed and then attached to one end of the receiver element with pressure sensitive tape along with a rupturable container containing an aqueous alkaline processing solution fixedly mounted on the leading edge of each element to form a film unit. A compressive pressure was applied to the container to rupture the seal at the end of the container and distribute its contents between the bleaching layer and the gelatin top layer of the photosensitive component. The aqueous alkaline treatment composition consists of the following ingredients:

【table】

[Table] Approximately 0.0030% of the treatment composition is removed by passing the film unit between a pair of pressure rolls into the illuminated area.
Distributed inch thick layers. The resulting laminate was kept in one piece and a multicolored one-piece negative-positive reflection print was formed. It showed good color quality and color separation. Example 12 Dye 18 was prepared as follows: Formula: 10 g of the xanthene dye represented by was suspended in 75 ml of dimethyl sulfoxide at room temperature under nitrogen gas. To this suspension was added 1.8 g of 50% sodium hydride dispersed in oil and the mixture was stirred at room temperature for 30 minutes.
A blue solution appeared. In this solution the structural formula: 10 g of the tosylate compound represented by was added, and the solution was stirred at room temperature for 3 hours. TLC on silica gel using 5/95 (by volume) methanol/methylene chloride showed no dye intermediate remaining. Methyl iodide (2ml) was added and the mixture was stirred for 1 hour. TLC showed completion of the reaction.
The reaction mixture was poured into 1 ml of water containing 1 ml of concentrated HCl to remove the precipitate. The precipitate was returned to water, stirred well, collected by filtration, and dried under reduced pressure to obtain 14.0 g. The product was dissolved in 400 ml of methylene chloride and 125 g of silica gel was added to the solution. The stirred mixture was poured into a sintered glass funnel and washed with methylene chloride. The dye was then extracted with 5/95 (by volume) methanol/methylene chloride and evaporated to dryness. This dye has the structural formula It is indicated by. 5.0 g of the dye thus produced was mixed with methylene chloride.
The 100 ml solution was added to a solution of 15 ml of boron trifluoride in 500 ml of methylene chloride under nitrogen and cooled to 5°C. The magenta solution was warmed to room temperature. TLC on silica gel showed 2 spots. A sample of this solution was heated to reflux,
No change appeared in the TLC results. Water was added dropwise to the solution and a magenta precipitate formed. The precipitate was collected, thoroughly washed with methylene chloride, and dried under reduced pressure at 80°C to obtain 9.0 g of solid. The solid was dissolved in a few drops of concentrated HCl-containing methanol, refluxed, and then dissolved in ether.
Injected into 1000ml. Take the precipitate, dry it,
3.8 g of product was obtained. This 3.8g sample was placed on 60g of sea sand together with methanol. The mixture was placed in a steel column and an additional 250 g of sea sand was added. The column was placed in a high pressure chromatography apparatus and washed with the following solvents (parts by volume): 1 methylene chloride 2 1/99 methanol/methylene chloride 4 2/98 methanol/methylene chloride 4 3/97 methanol /methylene chloride 12 5/95 methanol/methylene chloride 3 6/94 methanol/methylene chloride Appropriate solvent fractions were collected as determined by thin layer chromatography and evaporated to yield 1.8 g of dye developer. TLC of this material showed traces of impurities. The sample was again placed on 60 g of sea sand and returned to the steel column (which was first washed with 9/91 methanol/methylene chloride, by volume, and then with methylene chloride). The column was washed sequentially with the following solvents (parts by volume): 1 methylene chloride 3 2/98 methanol/methylene chloride 3 3/97 methanol/methylene chloride 1 4/96 methanol/methylene chloride 10 4/96 methanol /methylene chloride 3 6/96 methanol/methylene chloride Appropriate solvent fractions were collected as determined by thin layer chromatography and evaporated to yield 1.7 g of dye 18.
This was shown to be pure by TLC. The product is 553 nm in methyl cellosolve and ε=
It showed a maximum absorption of 117,500. NMR of this product
The spectrum confirmed its structure. Example 13 A film unit was constructed as follows: The photosensitive element consisted of an opaque subbed polyethylene terephthalate film base having the following layers applied thereon in sequence: (1) Sodium applied at a coverage of approximately 21 mg/m ² Cellulose sulfate layer; (2) Approximately 635 mg of the cyan dye developer used in Example 11/
cyan dye developer layer consisting of about 429 mg/m ² of gelatin, about 238 mg/m ² of dodecylaminopurine and about 128 mg/ ^{m 2 of} 4'-methylphenylhydroquinone; (3) about 1900 mg/m ² of silver and gelatin. Approximately 1140mg/ ^m2
Red-sensitive gelatino silver iodine bromide (1.8 micron) emulsion layer coated at a coverage of (4) 60-30- of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid.
Intermediate layer consisting of about 2000 mg/m ² of 4-6 quaternary polymer and about 30 mg/m ² of polyacrylamide; (5) about 666 mg/m ² of dye 18, about 323 mg/m ² of gelatin and about 150 mg/m of dodecylaminopurine ( ⁶ ) a green-sensitive silver iodobromide (1.11 micron) emulsion layer coated with a coverage of approximately 700 mg/m ² of silver and 308 mg/m ² of gelatin; (7) approximately 600 mg of silver; green-sensitive silver iodine bromide (1.8 micron) emulsion layer coated with a coverage of about 288 mg/m ² and gelatin; (8 ⁾ 60-30- of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid;
Intermediate layer consisting of about 1380 mg/m ² of 4-6 quaternary polymer and about 30 mg/m ² of polyacrylamide; (9) About 285 mg/m 2-phenylbenzimidazole
(10) A spacer layer consisting of about 820 mg/m ^{2 of} the yellow dye developer used in Example 11 and ^about 328 mg/m ² of gelatin; (11) Approximately 1050 mg/m ² of silver, 660 mg/m ² of gelatin and
4′-Methylphenylhydroquinone approx. 306mg/
(12) Overcoat layer of approximately 484 mg gelatin/m ^{2 .} The receiving element consists of a transparent undercoat of polyethylene terephthalate over which the following layers are applied in sequence: (1) Approximately 2450 mg/ft ² (26372
(2) butyl acrylate, diacetone acrylamide, styrene and methane ^; Acrylic acid 60-30-
4-6 quaternary polymer approximately 270mg/ft ² (2906mg/m ^{2 )} and polyvinyl alcohol approximately 30mg/ft ² (323
(3) about 10 mg/ft ² (108 mg/m ² ) of 1,4-butanediol diglycidyl ether and (a ⁾ 2 parts of polyvinyl alcohol and poly-4- 3 parts of a mixture with 1 part of vinylpyridine and (b) a graft copolymer of 4-vinylpyridine (4VP) and vinylbenzyltrimethylammonium chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC) (HEC/4VP/TMQ). ratio
2.2/2.2/1) 1 part of approximately 300mg/ft ² (3229mg/
( ⁴ ) a top layer of polyvinyl alcohol applied at a coverage of approximately 40 mg/ft ² (430 mg/m ² ); The magenta dye developer layer is dye 2 instead of dye 18.
A second film unit was made which was identical except that it contained about 540 mg/m ² of . The amounts of dyes 2 and 18 used in the film units were selected to provide substantially equimolar amounts of dye developer. That is, there were 617 x 10 ^-5 moles of Dye 18 (molecular weight 1011) and 617 x 10 ^-5 moles of Dye 2 (molecular weight 875) in each film unit. These film units are exposed on a sensitometer to a test exposure scale with white light, and then a subsequent layer of processing composition approximately 0.0030 inch thick is applied between the stacked photosensitive and receiver elements. Water 1622ml TiO ₂ 2312.0g Oximeated polydiacetone acrylamide
32.0g Potassium hydroxide (45% solution) 486.6g Benzotriazole 22.0g 4-Aminopyrazolo-(3,4d)pyrimidine
10.0g 6-Methyluracil 12.0g N-hydroxyethyl-N,N',N'-tris-carboxymethylethylenediamine 30.0g Polyethylene glycol (molecular weight 4000) 18.0g Bis(2-aminoethyl) sulfide 0.8g Colloidal silica ( 37.0g N-phenethyl-alpha-picolinium bromide (50% solids) 102.0g This treatment composition does not contain opacifying dyes, so the film units will be approximately 5.5g after applying the treatment composition. It was kept in the dark for a few minutes. The reflection density in the neutral region of the image is:

[Table] It was. It will be noticed that dye 18 gave a higher transmission density than dye 2. Dye 2 was determined to transfer at a slower rate than dye 18. Since the dye is insolubilized by the polymeric acid neutralization layer upon PH reduction performed after a predetermined period of time, it will be apparent that the difference in magenta transfer density is due to a combination of the difference in transfer rate and PH reduction. Another experiment is
We have shown that substantially similar transfer densities can be obtained even at slower density build-up rates if the PH is not reduced, ie, the neutralization layer is omitted. Similar experiments also showed that the transfer rate of Dye 2 was reduced by the presence of an opacifying dye, such as that used in Example 5, in the processing composition. The magenta image dyes provided by the present invention provide highly desirable spectral properties, in particular high green absorption and high blue transmission, together with high extinction coefficients, and are thus multicolored exhibiting improved reproduction of blue, green and pastel colors. It was found that the image was provided. Preferred magenta dyes of the invention have an absorption maximum at about 540 to 555 nanometers (dissolved in methyl cellosolve) and have a narrow band. It has been found that the dye developer of the present invention provides very good transfer control with very good delta values (detas) between maximum and minimum density. Generally, the dye developer transfer process is carried out in the presence of an auxiliary developer, such as 4'-methylphenylhydroquinone, but the dye developer of the present invention has very good performance without such an auxiliary developer. It has been found that it exhibits silver halide development properties and thus can reduce the total amount of auxiliary developer in a given system. This in turn reduces the contribution to smearing in the highlight areas of the transferred image due to oxidized auxiliary developer. Dye 2 and
It has also been found that the oxidized forms of these dye developers, exemplified in Example No. 18, exhibit large differences in alkali solubility compared to the unoxidized forms. The dye developers of the present invention exhibit strong resistance to post-processing transfer, such as solubilization and transfer after PH reduction, which imparts staining or "pinking" to highlight areas. The reasons for these desirable properties are not fully understood, but it is believed that the presence of a positive charge in combination with the nucleus is an important factor. Dyes of similar chromophore systems, commonly referred to as rhodamine or xanthene dyes, tend to exhibit fluorescence, an undesirable property. N-alkylation tended to increase fluorescence. The presence of phenolic groups, especially hydroquinonyl groups, is particularly
It has been unexpectedly found that fluorescence is reduced when X' is not hydrogen. In the example above, a neutralizing layer and a timing layer were placed between the image-receiving layer and its transparent support. In some embodiments, the neutralization layer and timing layer are formed using Edwin H. Advantageously placed in the photosensitive element, i.e. between the cyan dye developer layer and the opaque support, in the manner disclosed in U.S. Pat. No. 3,573,043 issued March 30, 1971 to Rand. . The image dye-providing material of the present invention was prepared by Howard G. It will also be appreciated that it may be used with film structures of the type disclosed in US Pat. No. 3,594,165 issued July 20, 1971 to Rodiers. All matter contained in the foregoing description is intended as an example and not as a limitation, as certain modifications may be made in the above-described products and methods without departing from the scope of the invention encompassed herein. It has no meaning.