JPH0115860B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of producing color photographic images by a dye diffusion transfer process. The present invention also provides novel non-diffusible dye-giving compounds that can be advantageously used in this process.
It also relates to photographic materials containing compounds. Among the various known methods for producing color photographic images according to the dye diffusion transfer process, the currently important method consists of the following steps. That is, it consists of using a non-diffusible dye-donor compound that is capable of image-wise releasing a diffusible dye or dye precursor product upon development and transferring this dye or dye precursor product to an image-receiving layer. It is something. Examples of dye-donor compounds suitable for this purpose include the non-diffusible color couplers described in DE 1095115. This known coupler releases "preformed dye" or "dye formed during the color coupling reaction" by reaction of the oxidation products of the first aromatic amine type color developer compound. It's something you get. The selection of necessary developer compounds is, of course, limited only within the range of color developing agents. Furthermore, in German Patent Application Publication No. 1930215,
A non-diffusible dye-donor compound in which a pre-formed latent diffusible dye group is linked via a releasable hydrazone group to a "group that imparts non-diffusible properties to the molecule" Are listed. The compound cannot be considered a color coupler. The selection of developer compounds used to release the diffusible dye groups is in no way limited to only within the range of common color developers;
Black and white developers (eg pyrocatechol) can also be used with advantage as well. German Patent Application No. 1772929 describes non-containing compounds having specific groups which can participate in a ring-forming oxidation reaction during development and leave off the "pre-formed dye groups" in the form of a diffusible substance. Diffusible colored compounds are described. The compounds described in DE 1772929 can be divided into two groups. Compounds belonging to the first group are those that require a conventional color developer compound during development, perform a coupling reaction with the oxidation product of the color developer, and then perform a coupling reaction with the oxidation product of the color developer, and in the subsequent ring-closing reaction. It is possible to leave off the dye groups previously formed in the form of a diffusible substance. Compounds belonging to the second group are those which can themselves be silver halide developers and therefore participate in the ring closure reaction in the form of oxidation products even in the absence of a separate developer compound. can release the diffusible dye. Furthermore, non-diffusible dye-donor compounds are also described in DE-A-2242762.
The compounds are sulfonamide phenol compounds and sulfonamide aniline compounds, which are capable of releasing the diffusible dye under the action of the alkali in the developer after the oxidation reaction that occurs during the development operation. . All of the above-mentioned known dye-donating compounds are used as compounds for forming negative images. In other words, when used with a conventional (negative image forming) silver halide emulsion, the diffusible dye is released during the development operation in a manner that is distributed in the shape of the resulting negative silver image. It is possible. Therefore, if a positive dye image is to be produced, it is necessary to use a direct positive-forming silver halide emulsion or to carry out a suitable reversal process. It is very difficult to select from known compounds a dye-donating compound that is very suitable in terms of all aspects such as reactivity and stability. The dye-donor compound should not release the diffusible dye during the entire duration of the actual alkaline development process, and should not undergo an "imagewise oxidation reaction" via the imagewise developed silver halide. It should be possible to release the diffusible dye only as a result of ``. On the other hand, the diffusible dye must be sufficiently rapidly released during the oxidation reaction that occurs in the form of the image and must be rapidly transferred.
Furthermore, the dye must be capable of being properly fixed onto the image-receiving layer, and the dye must have excellent optical spectral properties,
It must be light and heat resistant. The object of the present invention is to provide new non-diffusible dye-donor compounds having both suitable reactivity and good stability. Therefore, according to the present invention, an appropriate compound can be selected depending on the desired use from a series of compounds whose reactivity varies depending on the type of the leaving group. The present invention provides at least one method for producing color images according to a photographic dye diffusion transfer process.
An image on a photographic material having two light-sensitive silver halide emulsion layers and an associated "non-diffusible dye-donor compound capable of releasing the diffusible dye in an alkaline developer-containing medium when oxidized". A forming exposure is performed, followed by a silver halide developer (silver halide developer).
The dye-donor compound is oxidized by the oxidation product of this silver halide developer, and as a result of this oxidation reaction, the dye-donor compound is
alkali) to produce diffusible dyes distributed in the form of an image, characterized in that a non-diffusible dye-donor compound of the following formula is used: It is. In the above formula (), X represents a dye group or a dye precursor group. R <sub>1</sub> represents −OR <sub>4</sub> or −NHR <sub>5</sub> (here
R <sub>4</sub> represents hydrogen or a group which can be hydrolyzed under photographic development conditions, such as an acyl group; R <sub>5</sub> is hydrogen, an alkyl group, an aryl group, an acyl group or a heterocyclic group; <sub>R4</sub>
The alkyl group, aryl group, acyl group, and heterocyclic group mentioned in the definition of R <sub>5 and</sub> It may be an alkyl group, an aryl group, an acyl group, or a heterocyclic group that can be formed together with one of R <sub>3</sub> .
R <sub>2</sub> represents hydrogen, an alkyl group, an aryl group, or a heterocyclic group, and this alkyl group, aryl group,
The heterocyclic group may be one which, together with one of the substituents R <sub>1</sub> and R <sub>3</sub> , can form a 5- or 6-membered carbocyclicring or heterocycle; or R <sub>2</sub> represents a nitrogen atom having two substituents, the first substituent represents a group selected from the group consisting of hydrogen, an alkyl group, an aryl group, and an acyl group; may be capable of forming, together with R <sub>1</sub> , “a 5- or 6-membered heterocycle containing at least one nitrogen atom”; the second substituent may be hydrogen and “R <sub>3</sub> and represents a group selected from the group consisting of "groups that can be taken together to form a 5- or 6-membered heterocycle (preferably a pyrrole ring, a pyrazole ring, a pyridone ring),"
Two of the substituents bonded to the nitrogen atom are never hydrogen at the same time. R <sub>3</sub> is hydrogen, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a cyano group, or a “substituent R <sub>1</sub>
and R <sub>2</sub> together with one of 5-,
A group that can form a 6- or 7-membered carbocyclic ring or a heterocyclic ring. A group in which one or more of the substituents R <sub>1</sub> , R <sub>2</sub> , and R <sub>3</sub> is an alkyl group or contains an alkyl group. In this case, examples of the alkyl group include linear or branched groups containing 22 or less carbon atoms, and specific examples thereof include methyl group, ethyl group, isopropyl group, Examples include tertiary butyl group, n-butyl group, and octadecyl group.This alkyl group may have a substituent, and examples of such substituents include halogen, hydroxyl group, alkoxy group, carboxyl group, and sulfonate group. When one or more of the substituents R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> is an aryl group, this aryl group is a phenyl group. or a naphthyl group,
It may also have a substituent, and examples of such substituents include halogen, trifluoromethyl group, alkyl group, alkoxy group, alkylthio group, acylamino group, acyl group, carboxyl group, and sulfo group. It will be done. The acyl groups mentioned in the definitions of R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> include, unless otherwise specified, each of the following acyl groups: those derived from aliphatic or coaromatic carboxylic or sulfonic acids. acyl group;
Acyl group derived from carbonic acid or oxalic acid monoester: Acyl group derived from carbamic acid or sulfamic acid (which may have an alkyl or aryl group as a substituent at the nitrogen atom). When R <sub>4</sub> is a group that can be hydrolyzed under photographic development conditions, this group can be any "alkali labile group" or hydrolyzable group well known in the art, examples of which include: acetyl group, mono-, di- or trichloroethyl group,
Examples include perfluoroacyl group, pyruvyl group, alkoxyacyl group, and nitrobenzoyl group. This hydrolysable group R <sub>4</sub> may be a group that can be present as a substituent in one of the groups R <sub>2</sub> and R <sub>3</sub> . An example of such an R <sub>2</sub> group is a phenyl group having a carbonyl group in the ortho position, so that this substituted phenyl group is formally a benzoyl group (R <sub>4</sub> ). . When one or more of the substituents R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> is a heterocyclic group or a group containing a heterocyclic group, examples of such heterocyclic groups include is an aromatic-heterocyclic group (aromatic-heterocyclic group)
heterocyclic radicals) (e.g. pyridyl group,
(allyl group, thienyl group), and saturated heterocyclic groups (eg, piperidyl group, pyrrolidyl group, morpholyl group). The heterocycle in the dye-donating compound according to the present invention, which is formed by two of the substituents R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> , even if it is fused with another ring. For example, it may contain fused benzo rings. For example, if one of the substituents R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> is or bears an aryl or acyl group (e.g. benzoyl), this means that the remaining two
The two substituents can be taken together to form a heterocycle. Examples of heterocycles formed by R <sub>1</sub> and R <sub>2</sub> include:
Phthalyl ring, imidazoline ring, benzimidazoline ring, benzdiazinone ring (quinazolinone ring),
Examples include a benzoxazinone ring, a benzthiazole ring, and a benzoxazole ring. <sub>R2</sub> and <sub>R3</sub>
Examples of the heterocycle formed by the above include a quinolone ring, a pyridone ring, an indole ring, a pyrrole ring, a pyrazole ring, and a coumarin ring. Examples of the heterocycle formed by R <sub>1</sub> and R <sub>3</sub> include an indole ring, a pyrrole ring, a pyridone ring, and a thiazole ring. Examples of the heterocycle formed by R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> include fused rings such as a pyrazolobenzimidazole ring and a pyrazoloquinazolone ring. Alternatively, R <sub>2</sub> and R <sub>3</sub> may be taken together to form the atomic group necessary to complete a carbocycle (eg, a 5- or 6-membered carbocycle). Examples of such carbocycles include aromatic rings (eg, benzene rings). This ring may contain other substituents and/or "another ring fused to it"
It may also have . However, R <sub>2</sub> and
When R <sub>3</sub> forms an aromatic ring, R <sub>5</sub> is not an acyl group. Preferred examples of the dye-donating compounds according to the present invention include compounds having the following formula (). In formula (), R <sub>1</sub> has the meaning described above. R <sub>6</sub> represents an aryl group (eg phenyl group) or an acyl group. R <sub>7</sub> represents an alkoxy group or an alkyl group containing up to 22 carbon atoms, or an acylamino group or an arylamino group. These groups may be bonded to other groups, and this "other group" may also be present in the corresponding substituent in the pyrazolone color coupler, examples of which include alkoxy groups, alkylthio groups, etc. group, aroxy group, sulfo group, carboxyl group, acylamino group, sulfamyl group, and halogen. R <sub>1</sub> and R <sub>6</sub> can also be taken together to form a 5- or 6-membered heterocycle (preferably a benzimidazoline ring or a quinazolinone ring). Another preferred example of the dye-donating compounds according to the present invention is a compound having the following formula (). In formula (), R <sub>2</sub> is hydrogen, an alkyl group,
Represents an aryl group or a heterocyclic group. R <sub>8</sub> is an alkyl group (e.g. methyl group, isopropyl group, tertiary butyl group), an alkoxy group (e.g. methoxy group), a halogen (e.g. chlorine), a sulfamyl group (one of the hydrogens on the nitrogen atom in this group) one or two represent one or more substituents selected from the group consisting of a sulfo group (optionally substituted with an alkyl group or an aryl group), and a sulfo group. The compounds according to the present invention (hereinafter referred to as "enolamine or enediamine derivatives") may exist at least in part in the form of their tautomers, and therefore have the structural formula of the latter isomer. It can also be expressed. However, this means that
It does not apply to compounds where R <sub>4</sub> is a group other than hydrogen. It is noted that the dye-donor compounds according to the invention, as intact molecules, must not be able to diffuse into the layers in the photographic material. For this purpose, the compound contains a ballast group, for example one of the R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> groups.
It can be contained in Even when R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub> do not contain relatively long alkyl groups, the dye-donor compound can have good diffusion resistance. This is because even in such cases the molecule can be sufficiently large depending on the dye group. Alternatively, by selecting groups (R <sub>1</sub> , R <sub>2</sub> , R <sub>3</sub> ) of appropriate size, it is possible to impart sufficient diffusion resistance to the dye-donor compound. Ballast groups are groups that make it possible to add the compounds according to the invention in the form of non-diffusible substances into the hydrophilic colloids commonly used in photographic materials. Preferred ballast groups are generally organic groups containing straight or branched aliphatic groups. The organic group may be aromatic, homocyclic, or heterocyclic, generally having 8 to 20 carbon atoms. These groups can be attached directly or indirectly to the remaining part of the molecule, for example via the following groups:-
NHCO-, <sub>-NHSO2-</sub> , -NR- (wherein R is hydrogen or an alkyl group), -O-, -S-. In the case of the compounds of the invention, the substituents R <sub>1</sub> , R <sub>2</sub> and R <sub>3</sub>
At least one of these or "the heterocycle formed by two of these substituents" may have a ballast group. The ballast group may contain water-solubilizing groups (eg sulfo groups, carboxyl groups; the groups may also be present in anionic form). Diffusivity depends on the size of the whole molecule of the compound, so in some cases, for example, when the whole molecule has a sufficiently large size, relatively short groups can be used as ballast groups. It is also possible. In general, any type of dye group can be used as a suitable dye group. However, this dye group must have sufficient diffusibility to diffuse through the photosensitive material layer toward the image-receiving layer. For this purpose, one or more water-solubility-imparting groups can be attached to the dye group. Examples of suitable water solubility-imparting groups include carboxyl groups, sulfo groups, sulfonamido groups, aliphatic or aromatic hydroxyl groups. However, the sulfonamide group that remains in the dye after the molecule decomposes gives the dye molecule the property of diffusing well in alkaline media, so the presence of a separate water-solubility-imparting group is never necessary in this case. Not a necessary condition. Examples of dyes that can be used particularly advantageously in the method of the invention include azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, metal complex dyes, and colored metal complexes. The term “dye precursor group” as described herein
means “a dye that can be converted into a dye by oxidation reactions, coupling reactions, or reactions that release an auxochrome in a chromophoric system (e.g., a hydrolysis reaction) in a routine step or in a separate step during the carrying out of a photographic processing operation. It refers to the residue of a chemical compound. Examples of dye precursors that meet this definition include lyuko dyes, couplers, and "dyes that are converted to another type of dye during processing." Since the distinction between dye groups and dye precursor groups is not essential, the dye precursor groups will also be included in the general term "dye group" in the following description. Next, the chemical formula of a preferred specific example of the dye-donating compound according to the present invention is shown. Production of dye-donating compound 2 Compound produced according to the production method described below ()
4.9 g was suspended in 50 ml of pyridine, and then 4.3 g of sulfochloride of the dye of the following formula was added. The solution was heated to 45°C and then allowed to cool. After adding 50 ml of water, the solution was stirred for 1 hour. The precipitate was separated by suction filtration and washed with water. The residue was suspended in acetone, filtered off with suction, washed with acetone and dried. Yield of compound 2: 5.2
g. Compound () has the following formula, and was produced according to the production method described below. The following formula of pyrazolobenzimidazole in glacial acetic acid.
suspended in 150 ml and then at room temperature.
An aqueous solution of 3.3 g of NaNO <sub>2</sub> (the amount of water was 12 ml) was added dropwise. This suspension was then stirred for 2 hours and then added to an aqueous solution of 22.6 g of Na-dithionite (water amount 150 ml) and then stirred for 30 minutes. The product separated by suction filtration was washed with water. The residue was suspended in 250 ml of methanol and then water was added.
250ml was added. The product was then heated to its boiling point, cooled, filtered off with suction, washed with methanol and dried under nitrogen. Yield: 18.2g. Compounds 1 and 3 were prepared by reacting compound () with a sulfochloride of a dye of the following formula, following the same method as for compound 2. and Production of dye-donor compound 4 Compound ()4.4 produced according to the production method described below
g in 50 ml of pyridine, then compound 2
4.3g of the same dye sulfochloride used in the production of was added. This mixture
Heat to 40℃ until solution state, then at 40℃
Stirred for 15 minutes then cooled. 50 ml of water was added dropwise, and the precipitate was separated by suction filtration and washed with water. The residue was suspended in acetone, filtered off with suction, washed with a little acetone and dried. Yield of compound 4: 5g. Compound () has the following formula, and was manufactured according to the following manufacturing method. 6.2 g of compound () (manufacturing method will be described later) was suspended in 170 ml of glacial acetic acid, and 9 g of zinc dust was added.
was added little by little. The entire reaction mixture was stirred at room temperature for 1 hour and then at 40° C. for 30 minutes, filtered off with suction and washed with glacial acetic acid. Concentrate the mother liquor under vacuum and remove the greasy residue with methanol.
Stirred together with 50 ml, filtered with suction, washed with methanol and dried under nitrogen. The yield of compound () was 5 g. Compound () has the following formula, and was produced according to the production method described below. The following formula 9 g of pyrazoloquinazolone were suspended in 75 ml of glacial acetic acid, then 1.65 g of NaNO <sub>2</sub> was added and the mixture was stirred for 4 hours to effect a positive nitrite reaction. After standing overnight, the product was separated by suction filtration,
Washed with <sub>H2O</sub> and dried. The yield of compound () was 7.7 g. Preparation of dye-donor compound 39 First step: 2-Methyl-4-octadecylphenol 1-octadecene was reacted with excess o-
Reacted with cresol. The product was distilled under reduced pressure and then chromatographed on a column of silica gel using toluene as eluent. The first fraction, 6.2 g, is <sup>1</sup> H−
The NMR spectrum identified it as 2-methyl-6-octadecylphenol, and the second fraction, 15.3 g, was 2-methyl-4-octadecylphenol. Second step: 2-Amino-6-methyl-4-octadecylphenol Aniline in 50 ml methanol and 8 ml concentrated hydrochloric acid
2.7 g of the solution was diazotized by dropwise addition of a solution of 2 g of sodium nitrite in 4 ml of water at -5 to 0°C. 6 g of sodium acetate in 100 ml of methanol
-Methyl-4-octadecylphenol (second fraction of the first stage) was added to a solution of 10.4 g. The solution of diazonium salt prepared above was heated at 5°C.
and an oily phase formed. After stirring for 3 hours,
Add 600ml of acetone to the solution mixture,
Upon addition of 1.35 g of sodium acetate, 1.35 g of aniline diazotized as described above was also added. After stirring for an additional hour, the liquid phase was separated from the precipitate and the solvent was removed under reduced pressure. The oily residue was heated with 100 ml of methanol. After cooling, the solvent was decanted from the oily phase and the residue was dissolved in 100 ml of acetic acid. 14.1 g of zinc dust was added to the solution and after stirring for 10 minutes, the mixture was filtered with suction and the residue was dissolved in acetic acid.
Washed with 50ml. The mother liquor and washings were mixed with 200 ml of water and the product was extracted with 100 ml of methylene chloride. The organic phase was washed twice with water and then the solvent was removed in a rotary evaporator. Yield: 7.8 g (72%) of 2-amino-6-methyl-4-octadecylphenol (oil). Third stage: magenta dye sulfochloride (R=
Cl) 12.2 g (0.018 mol) of magenta dye sulfonic acid (R = -ONa) with a purity of 89.7% (including inorganic salts),
It was added to a mixture prepared from 110 ml of chloroform, 5.5 ml of phosphoryl chloride and 11 ml of dimethylformamide while cooling to 20°C. The mixture was heated to boiling for 5 minutes and continued stirring overnight without further heating. Precipitation of dye sulfochloride 20
The mixture was filtered under suction at ℃, washed with 50 ml of chloroform, and used while still wet for the next reaction. Step 4: Compound 39 0.018 mol of freshly prepared magenta dye sulfochloride (product of step 3) and pyridine 4
ml (0.05 mol) was added to a solution of 7.5 g (0.02 mol) of 2-amino-6-methyl-4-octadecylphenol (product of the second stage) in 80 ml of methylene chloride. The reaction was complete after stirring for 3 hours. After removing the solvent under reduced pressure, the residue was dissolved in 50 ml of acetic acid and the solution was added dropwise to 400 ml of water with stirring.
The precipitate was filtered off with suction, washed with water and dried. Calcium chloride solution of product in 100 ml of methylene chloride
10 g and 10 g of Fuller's earth for 30 minutes,
It was then filtered with suction and the filter cake was washed with 50 ml of methylene chloride. The combined solution was concentrated to 50 ml and stirred at room temperature for 2 hours. The dye precipitate was filtered off with suction, washed with 15 ml of methylene chloride, then triturated with cyclohexane, filtered off again, washed with cyclohexane and dried. Yield: 5.4 g of compound 39 (32% of theory). It is of course possible to produce the compounds of the present invention according to various other production methods. For example, a suitable starting compound is coupled with a diazonium salt, a reduction reaction is carried out according to known reduction methods to form the corresponding enolamine or enediamine or its tautomer, and then the dye It is also possible to produce the compounds according to the invention by reacting them with sulfochlorides. The dye-donor compounds according to the invention can be added to casting solutions for forming layers of photographic materials according to any known method. The amount of dye-donor compound used per casting liquid can vary within relatively wide limits. The most suitable concentration in each individual case can be determined by simple tests. For example, 5 to 80 g, preferably 20 to 40 g (per casting liquid) of this dye-donor compound can be used. In order to obtain the desired effect, it is necessary to use this non-diffusible dye-donor compound in combination with silver halide; for this purpose, the non-diffusible dye-donor compound is combined with the water-solubility imparting compound present therein. The compound can be added to the casting liquid by making an alkaline aqueous solution using the group and adding this aqueous solution to the casting liquid. The non-diffusible dye-donating compound can also be added to the photographic layer according to any known emulsification method. Addition methods of this type are described, for example, in British Patents No. 791219, No. 1099414;
It is described in the specification of No. 1099417, etc. Also,
It is also possible to make an aqueous dispersion of the dye-donor compound and add this to a given casting liquid. For this purpose, the aqueous dispersion of the dye-donor compound is dispersed more finely by vigorous stirring in the presence of sharp-edge sand or by the use of ultrasound. It can be made into a dispersion. According to another preferred embodiment, the following operations can be advantageously carried out.
The dye-donor compounds can also be added to the photographic layer in the form of so-called microcapsules, together with the silver halide and, if desired, also with the developer. In this case, two or more types of light-sensitive silver halide emulsions with different sensitivities and a corresponding non-diffusible compound are combined into a so-called mixed emulsion (mixed grain emulsion) as described in U.S. Pat. No. 2,698,794, etc. −grain emulsions)
They can be combined together in a single layer according to the method of preparation. For example, a blue-green dye-releasing compound can be combined with a red-sensitive layer, a magenta dye-releasing compound can be combined with a green-sensitive layer, and a yellow dye-releasing compound can be combined with a blue-sensitive layer. As used herein, the terms "combination,""association," and "associated" refer to the formed silver image and
In order to maintain imagewise consistency between the free diffusible dye and the dispersed dye distributed according to the shape of the image,
It means suitably arranging the silver halide emulsion and the dye-donor compound with respect to each other such that they are capable of interaction. Most preferably, the "associated dye-donor compound" is added to the silver halide emulsion layer itself or to a layer adjacent to the silver halide emulsion layer. The "adjacent layer" is preferably located behind the silver halide emulsion layer ("rear" when viewed from the direction of the incident light beam during exposure). The dye-donor compounds of this invention are image-wise oxidized by the oxidation products of the developer during silver image-forming development and then undergo an elimination reaction under the action of an alkali in the developer or activator. (decomposition reaction) occurs and the dye group is released in the form of a diffusible substance such as a sulfonamide of the dye. Known photographic developer compounds can be used for this development.
However, the developer compound must be capable of oxidizing the dye-donor compound according to the invention when in its oxidized product form. Examples of suitable developers include: Hydroquinone N-Methylaminophenol 1-Phenyl-3-pyrazolidone 1-Phenyl-4,4-dimethyl-3-pyrazolidone Aminophenol N,N-diethyl-p-phenylenediamine N-ethyl-N-hydroxyethyl-p- Phenylenediamine 3-Methyl-N,N-diethyl-p-phenylenediamine N,N,N',N'-tetraalkyl-p-phenylenediamine (e.g. tetramethyl-p-phenylenediamine) Triethylsulfobutyl -p-phenylenediamine 1,4-bis-pyrrolidinobenzene reductones The selection range of developing agents used in the method of the invention is:
Note that it is by no means limited to only within the scope of color developing agents. Common black and white photographic developers can also be used. Black and white photographic developer is
It has the advantage of having a low tendency to discolor. in fact,
The developer may be present in a layer in the color photographic material, in which case the developer is activated in the layer by an alkaline activator solution, or in an alkaline processing solution or paste. is activated. If the dye-donor compounds according to the invention are those which themselves also have an action as developer, it is not necessary in individual cases to use auxiliary developer compounds. In such a case,
This dye-donor compound is developable
Oxidized directly by silver halide. During the development process, diffusible dyes are released in an image-wise distribution;
If a positive color transfer image is to be produced, a direct positive silver halide emulsion must be used.
On the other hand, when an ordinary negative emulsion is used, a suitable reversal process must be carried out. This type of reversal process can be implemented using a silver salt diffusion process. A method of producing a positive color image by performing a photographic reversal operation according to a silver salt diffusion process using a known color coupler is described, for example, in U.S. Pat.
It is described in the specification of No. 2763800, etc. When the dye-donating compound according to the present invention is used in place of the above-mentioned known coupler, a photosensitive element (photosensitive material) suitable for use in the dye diffusion transfer method of the present invention is obtained. Photosensitive elements of this type are composed, for example, of a light-sensitive silver halide emulsion layer and an associated binder layer containing development nuclei for a physical development process and a dye-donor compound. It may have at least one combination. During the development operation, exposed parts of the silver halide are chemically developed in the light-sensitive silver halide emulsion layer. unexposed area
part) is transferred by means of a silver halide solvent to an associated binder layer containing development nuclei, where it is physically developed. When physical development is carried out using a developer that can produce oxidation products capable of releasing the diffusible dye by reaction with the dye-donor compounds present in the layer, the diffusible dye is distributed in the shape of the image. This can then be transferred to an image-receiving layer, where a positive color image is produced. When reversal operations are carried out using compounds capable of releasing development inhibitors in an image-wise distribution, the light-sensitive element used is in "unexposed" contact with the light-sensitive silver halide emulsion layer. and a second emulsion layer containing said dye-donor compound. For example, the light-sensitive silver halide emulsion layer is developed with a color developer in the presence of a "compound that releases a development inhibitor upon reaction with the oxidation product of the color developer." The development inhibitor released into the photosensitive layer according to the shape of the image diffuses toward the "adjacent emulsion layer that can be developed without exposure", where it is distributed according to the shape of the image. to suppress development. The uninhibited areas (positive areas) in the emulsion layer that can be developed without exposure to light are developed by the residual developer, and the oxidation products of this developer are then converted into non-diffusible dye-donor compounds of the present invention. to release a diffusible dye, which is then imagewise transferred to the image-receiving element. Preferred examples of compounds that release development-inhibiting compounds during reaction with oxidation products of color developing agents include the well-known DIR
A coupler (a coupler capable of releasing a development inhibitor) can be mentioned. This DIR coupler is a color coupler that contains a releasable inhibitor group in its coupling position. This type of DIR coupler is described in US Pat. No. 3,227,554 and elsewhere. Another example of a compound capable of releasing a development inhibitor upon reaction with the oxidation product of a color developer includes the compounds described in US Pat. No. 3,632,345 and the like. The compound is not a color coupler. Therefore, no dye is produced when the development inhibitor is released. DE 1229389 describes non-diffusible substituted hydroquinone compounds which can be used advantageously in processes of this type. This substituted hydroquinone compound is oxidized to the corresponding quinone upon reaction with the oxidation product of the developer, thereby releasing the mercaptan development inhibiting compound. Examples of suitable direct positive silver halide emulsions include:
A positive silver image can be generated with just one development,
There are also various direct positive silver halide emulsions capable of producing oxidation products of the developer in a distribution state corresponding to the shape of the positive silver image. For example, exposure or chemical processing may result in a developable fog, and this fog may disappear in image form during imagewise exposure under certain conditions. It is possible to use silver oxide emulsions. This fog remains in the unexposed areas, thus producing a direct positive silver image during subsequent development operations. When the dye-donor compounds of this invention are used with the direct positive silver halide emulsions described above, a diffusible dye will result whose distribution conforms to the shape of the silver image. Another example of a direct positive silver halide emulsion that can be used in accordance with the invention is a so-called nufogged direct positive silver halide emulsion that is sensitive primarily to the inside of the silver halide grains. can give. When imagewise exposed to this type of emulsion, a latent image
occurs mainly inside the silver halide grains. However, the development of this type of fog-free direct positive silver halide emulsion is carried out under fog-forming conditions, and during development, fog occurs primarily in the unexposed areas, resulting in a positive silver image. This fog-free direct positive silver halide emulsion is characterized by the use of a common surface developer, such as a developer composition having the following composition: p-hydroxyphenylglycine 10 g Sodium carbonate (crystals) 100 g Water When developed with a total residual volume of 1000 ml, the exposed sample preferably produces no or only a very low density silver image, whereas an internal developer of the following composition: Materials: Hydroquinone 15g Monomethyl-p-aminophenol sulfate
15 g Sodium sulfite (anhydrous) 50 g Potassium bromide 10 g Sodium hydroxide 25 g Sodium thiosulfate (crystals) 20 g Water Balance total When using 1000 ml, a silver image of appropriate density will be produced. Selective fogging operations on nonfogging direct positive emulsions that have been image-formingly exposed.
fogging) can be carried out by treatment with a fogging agent before or during the development operation. Suitable fogging agents are reducing agents such as hydrazine, substituted hydrazines. Regarding this point, please refer to US Pat. No. 3,227,552 and the like. Examples of fog-free direct positive emulsions include silver halide emulsions with internal faults in the silver halide grains (see U.S. Pat. No. 2,592,250), and layered grain structures.
(See German Patent Application Publication No. 2308239). The various emulsions described above can be subjected to chemical sensitization. This chemical sensitization can be carried out, for example, by adding sulfur-containing compounds such as allyl isothiocyanate, allylthiourea, sodium thiosulfate, etc. during the ripening operation of the emulsion. Further examples of suitable chemical sensitizers include reducing agents, such as the tin compounds described in Belgian Patent Nos. 493464 and 568687; polyamines (such as diethylenetriamine, aminomethane sulfinic acid derivatives; Belgian Patent No. 547323); Please refer to the specification etc.). Other suitable chemical desensitizers are noble metals and noble metal compounds, such as gold, platinum, palladium, iridium, ruthenium, rhodium and their compounds. This type of chemical sensitization method is described in R. Koslowski's paper [Z.Wiss.Phot. Vol. 46, p. 65-
72 (1951)]. The emulsion can also be sensitized with polyalkylene oxide derivatives; examples of this type of sensitizer include: molecular weight 1000-20000;
polyethylene oxide; condensation products of alkylene oxides with aliphatic alcohols, glycols, dehydration cyclization products of hexitols, alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines or aliphatic diamines. The molecular weight of this condensation product is at least 700, preferably 1000 or more. Of course, it is also possible to use these sensitizers in combination with each other in order to obtain a specific effect.
This is true for example in Belgian patent no. 727982,
No. 537278 and British Patent No. 727982. It is also possible to subject this emulsion to spectral sensitization (optical sensitization). Examples of sensitizers that can be used for this purpose include: common monomethine or polymethine dyes, such as acidic or basic cyanine, hemicyanine, streptocyanine, merocyanine, oxonol, hemioxonol, styryl dyes. ; other trinuclear or polynuclear methine dyes, such as rhodacyanine, neocyanine. This type of sensitizer is described, for example, in the book The Cyanine, Soybean, and Related Compounds by F. M. Harmer (1964) (published by Interscience, Publishers, John, Willey, & Sons). There is. The emulsion may contain conventional stabilizers,
Examples of such stabilizers include: homopolar or salt-type compounds containing mercury and aromatic or heterocycles, such as mercaptotriazole; simple mercury salts; sulfonium-mercury double salts; Other mercury compounds. Another suitable stabilizer is azaindene, preferably tetra- or penta-azaindene, more preferably azaindene substituted by a hydroxyl group or an amino group. Compounds of this type are described in the article by Beer [Z. Wiss. Phot., Vol. 47, pp. 2-27 (1952)]. Further examples of suitable stabilizers include: heterocyclic mercapto compounds such as phenylmercaptotetrazoles, quaternary benzthiazole derivatives,
Benztriazole etc. Preferably, gelatin is used as the binder for this photographic layer. However, instead of gelatin (or parts thereof) other natural or synthetic binders may be used. Examples of such natural binders include: alginic acid and its derivatives, such as its salts, esters, amides; cellulose derivatives, such as carboxymethyl cellulose, alkyl cellulose (e.g. hydroxyethyl cellulose); starch or its derivatives, e.g. Ethers, esters; caragenates. Examples of synthetic binders include polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, and the like. This hardening of the photographic layer can be carried out according to conventional methods.
Examples of hardeners include: formaldehyde; halogen-substituted aldehydes containing carboxyl groups, such as mucobromic acid.
acid); diketone; methanesulfonic acid ester;
dialdehyde. Other examples of hardeners include fast acting hardeners such as carbodiimide hardeners, carbamoylpyridinium salts, carbamoyloxypyridinium salts. In this regard, reference is made to German Patent Application Nos. 2263062, 2225230 and 1808685. The dye diffusion transfer method of the present invention comprises: a photosensitive element comprising one or more silver halide emulsion layers and an associated non-diffusible dye-donor compound; An image receiving element adapted to produce a predetermined dye image with a color dye. For this purpose, the photosensitive element and the image-receiving element are
They must be in close contact with each other for at least a certain period of time during the development operation. This contact operation allows the diffusible dye produced in an imagewise distribution within the photosensitive element during development to be transferred to the image-receiving layer. This adhesion (contact) operation can be performed after the development operation has started. Alternatively, this close contact operation may be performed before the start of the developing operation. For example, photographic materials in which the photosensitive element and the image-receiving layer are in the form of an integrated unit (hereinafter referred to as "one-sheet materials").
It is also possible to carry out the dye diffusion transfer process using a sheet material) in which both elements remain intact after development is complete. In other words, the photosensitive element is not separated from the image-receiving layer even after dye transfer. A specific example of this type of photographic material can be found in German Patent Application Publication No.
It is described in No. 2019430 etc. Examples of one-sheet materials that can be advantageously used to carry out the dye diffusion transfer method according to the invention include those having the following layered elements: (1) a transparent base layer (support layer); (2) an image-receiving layer; (3) a light-opaque layer; (4) at least one light-sensitive silver halide emulsion layer and at least one non-diffusible dye donor associated therewith. A photosensitive element comprising a compound (5) a retarding layer (6) an acidic polymer layer (7) a transparent base layer. Such one-sheet materials are made up of two
It may also be created by combining two parts. That is, it may consist of a photosensitive part (layered elements (1) to (4)) and a cover sheet part (layered elements (5) to (7)), and these two parts are stacked together in a layered manner. do.
If desired, spacer strips may be used to provide a predetermined amount of hydraulic fluid (chemical,
A space can be provided between the two parts for accommodating a liquid (e.g. developer). layered elements
(5) and (6) together form a neutralizing system, but the order of arrangement of these layers may be reversed and placed between the base layer and the image-receiving layer of the photosensitive section. A supply means can be provided for supplying the working fluid between the photosensitive section and the cover sheet section. For example, a horizontally arranged openable container (splittable)
a supply means in the form of a container) may be provided;
The container may thus be such that, when a mechanical force is applied, the liquid within the container can be delivered between two adjacent layers in the one-sheet material. One of the important parts of the photographic material according to the invention is the photosensitive element. One step dye transfer process
The photosensitive element used in the -dye transfer process may include a light-sensitive silver halide emulsion layer and an associated non-diffusible dye-donor compound. The non-diffusible compound may be present in a layer adjacent to the silver halide emulsion layer or may be included within the silver halide emulsion layer itself.
In the latter case, the color of the image-forming dye is preferably selected so that the main absorption spectral range of the dye-donating compound and the main sensitivity spectral range of the silver halide do not coincide. However, multicolored transfer images with natural colors
In order to produce images), the photosensitive element is provided with three combinations of ancillary dye-donor compounds and photosensitive silver halide emulsions meeting the above conditions, and in which case generally colored The absorption spectral range of the compound used may substantially correspond to the sensitivity spectral range of the corresponding silver halide emulsion layer. However, in such cases the coloring combination must be placed in a separate layer behind the silver halide emulsion layer to ensure the highest sensitivity (see above). ``Backward'' is the ``backward'' when viewed with reference to the rear of the incident light during exposure). The "developing agent oxidation products" produced during development of the silver halide emulsion must act only on the desired accompanying dye-donor compound. Therefore, photosensitive elements generally include separation layers to ensure that the oxidation products of the developer do not diffuse into other layers (i.e., non-associated layers).
can be provided. This separating layer may, for example, contain suitable substances capable of reacting with the oxidation products of the developer, for example non-diffusible hydroquinone derivatives. When the developer is a color developer, the isolation layer may include a non-diffusible color coupler. Accordingly, according to a preferred embodiment of the invention, a photosensitive element can be prepared having the following structure (indicating the order of arrangement of each layer). Blue-sensitive silver halide emulsion layer A layer containing a non-diffusible compound capable of releasing a diffusible yellow dye Separation layer Green-sensitized (green-sensitive) silver halide emulsion layer A non-diffusible compound capable of releasing a diffusible purple dye A layer comprising: A separating layer; A red-sensitized (red-sensitive) silver halide emulsion layer; A layer comprising a non-diffusible compound capable of releasing a diffusible blue-green dye; Of course, these silver halide emulsion layers may be arranged in a different order. However, in that case, the order of the associated layers containing coloring systems must also be varied to ensure that the desired layer combination is maintained. The light-opaque layer arranged below the photosensitive element is permeable to the processing liquid, which is an aqueous alkaline solution, and therefore permeable to the diffusible dye. This light-opaque layer mainly consists of the following two
It plays two roles. One is the image silver that remains on the original photosensitive element after development.
silver) and the remaining dye-donor compound as a color negative, so that only the positive dye transfer image is visible through the transparent base layer of the photosensitive area. The second role is to shade the photosensitive element on the underside of one side of the image-receiving layer. This role is particularly important when: This is particularly important where the one-sheet material is contacted with an alkaline processing mass within the camera itself after exposure and then removed from the camera and developed outside the camera. Layers that are transparent to diffusible dyes but sufficiently block light can be produced using, for example, the following materials:
A dispersion of an inorganic or organic dark pigment, preferably a black pigment, such as a dispersion made by dispersing carbon black in a suitable binder, such as a gelatin solution. Generally, a layer containing 10 to 90% by weight (based on total dry weight) of carbon black in gelatin and having a layer thickness of 0.5 to 2 microns will ensure sufficient light blocking properties during development. Although the particle size of the pigment used here is not a critical condition, it is 0.5μ
Pigments having a particle size substantially exceeding the above are not preferred. This light-opaque layer preferably includes a white pigment layer below the black pigment layer in addition to the black pigment layer. The role of this white pigment layer is to cover the black layer and provide a white background for the image. Various white pigments can be used for this purpose. However, the white pigment must have sufficient covering power at a layer thickness that is not too large. Examples of suitable white pigments include: barium sulfate; zinc, titanium, silicon;
Oxides of aluminum and zirconium; barium stearate; kaolin. It is preferable to use titanium dioxide as this white pigment. The white pigment must fully meet the same conditions with respect to binder, concentration and particle size as those imposed on the black pigment. The thickness of this white pigment layer can be varied depending on the desired whiteness of the background. Preferably, the white pigment is used as a layer with a layer thickness of 5 to 20 microns. In the present invention, instead of using the above-mentioned light-opaque layer itself, "means for producing this kind of light-opaque layer" may be placed between the photosensitive element and the image-receiving layer in the one-sheet material. It is possible. This means of production can be, for example, a clouding agent.
It may be a laterally disposed container with a hydraulic fluid containing an agent (for example a pigment). And this container
The liquid within the container may be released between the two layers upon application of mechanical force to form the desired pigment layer between these layers. The image-receiving layer has as an essential component a binder containing dye mordants for fixing the diffusible dye. Preferred mordants for acid dyes are long-chain quaternary ammonium or phosphonium compounds and tertiary sulfonium compounds, and specific examples of these compounds include those described in U.S. Pat. Nos. 3,271,147 and 3,271,148. It will be done. Metal salts and their hydroxides which can form substantially insoluble compounds by reaction with acidic dyes can also be used. These dye mordants can be dispersed in conventional hydrophilic binders (eg, gelatin, polyvinylpyrrolidone, fully or partially hydrolyzed cellulose esters, or the like) in the image-receiving layer. Certain binders can also act as mordants, examples include: copolymers and polymer mixtures of vinyl alcohol and N-vinylpyrrolidone (e.g. polymers of nitrogen-containing quaternary bases, such as polymers of N-methyl-2-vinylpyridine (see, for example, U.S. Pat. No. 2,484,430). Another example of a binder having a preferable mordant action is a guanylhydrazone derivative of an acylstyrene polymer as described in German Patent Application No. 2009498 and the like. However, other binders, such as gelatin, will generally be added to the last-mentioned type of binder. Transparent substrates suitable for use in one-sheet materials according to the invention may be any transparent substrate commonly used in the photographic field, including cellulose esters, polyethylene terephthalate, polycarbonates, or other transparent substrates. Examples include films made of film-forming polymers. In the photosensitive element, an alkaline processing agent is used to adjust a relatively high pH value (about 11-14), thereby initiating development and dye diffusion in the form of an image. The dye, and the image produced, are not particularly stable at such PH values. Therefore, after development is complete, the photographic material must be rendered substantially neutral or slightly acidic. This purpose was achieved by applying a separate acidic polymer layer (acid) to this photographic material according to known methods.
This can be achieved by providing a polymer layer). However, this acidic polymer layer must act only gradually on the alkaline processing agent during development. Examples of acidic polymer layers that can be used in the present invention include binder layers containing polymeric compounds having acidic groups (eg, sulfo groups, carboxyl groups). This acidic group reacts with the cation of the alkaline treatment agent to form a salt, and this reaction mechanism lowers the PH value of the treatment agent. Of course, this polymeric compound (ie the acid group) is added to the layer in the form of a non-diffusible substance. In many cases, the acidic polymer may be a derivative of cellulose or a derivative of a polyvinyl alcohol compound, but it is also possible to use other polymeric compounds. Examples of suitable acidic polymers include: cellulose derivatives with free carboxyl groups, such as cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate,
ethyl cellulose acetate hydrogen succinate,
Cellulose acetate hydrogen succinate hydrogen phthalate; cellulose ethers and -esters modified with dicarboxylic or sulfonic anhydrides (e.g. o-sulfobenzoic anhydride);
Carboxymethyl cellulose; polystyrene sulfonic acid; polyvinyl hydrogen phthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid; aldehydes substituted by carboxyl or sulfo groups (e.g. o-, m- or p-benzaldehyde sulfonic acid or -carboxylic acid) and polyvinyl Acetals obtained by reaction with alcohols; partially esterified ethylene/maleic anhydride copolymers; partially esterified methyl vinyl ether/maleic anhydride copolymers and their analogs. This acidic copolymer layer contains acidic groups in an amount sufficient to reduce the original pH value of the alkaline treatment agent from 11 to 14 to substantially neutral or weakly acidic (PH value of 5 to 8). Must have. In order to delay the time when the pH value decreases, this acidic polymer layer can be coated with a so-called retard layer according to known methods. The retard layer is an alkali-permeable layer and is preferably comprised of a polymer inert to alkali, such as polyvinyl alcohol or partially acetalized polyvinyl alcohol. The extent of the delay in the PH value drop can be determined by appropriately selecting the thickness and composition of this retard layer.
Can be adjusted as desired. An example of a retard layer comprising a polymer with good permeability properties is the retard layer described in German Patent Application No. P2455762.8. A neutralizing member (neutralizing type) consisting of a combination of an acidic polymer layer and a retard layer is described in German Patent No. 1285310 and the like. A combination of layers of this type can be present in the photographic material of the invention,
For example, it can be placed between a transparent base layer and an image-receiving layer in the photosensitive area. Alternatively, it is also possible to arrange a neutralizing member consisting of an acidic polymer layer and a retard layer on the cover sheet part. Of course, the two layers, the acidic polymer layer and the retard layer, must be arranged in such a sequence that the alkali in the alkaline treatment agent can first pass through the retard layer and then reach the acidic polymer layer. . The dye diffusion transfer method according to the invention can be advantageously carried out in or using a suitable self-developer camera. For example, the following members can be installed in this camera. That is, a member that supplies a working fluid between the photosensitive element and the cover sheet portion after the photosensitive element is exposed to light, and a member that performs a masking action to provide light-shielding properties to the photosensitive material can be disposed. This type of camera is preferably provided with two squeeze rolls in contact with each other. In this case, the following operations can be performed. That is, the one-sheet material is passed between these two squeeze rolls, thereby opening the laterally arranged container and dispersing the contents (medicinal solution) of the container into a predetermined layer in the one-sheet material. It can be supplied between After passing through the squeeze roll, both sides of the photosensitive element are protected by a light-opaque layer, which prevents unwanted light leakage, so that the exposed photographic material can be removed from the camera immediately after the start of development. To process the one-sheet material after imagewise exposure, the photosensitive element is contacted with a working fluid, which is an aqueous alkaline solution. The imagewise exposed silver halide emulsion layer is developed in the presence of a developer compound, producing oxidation products of the developer in a distribution consistent with the shape of the positive silver image produced.
This oxidation product oxidizes the accompanying coloring compounds, which release a diffusible dye by reaction with the alkali in the activator. This alkaline aqueous hydraulic fluid may contain a thickening additive (eg hydroxyethyl cellulose). This working fluid also contains development accelerators, stabilizers, silver salt solvents, fogging agents,
Antioxidants and other additives may also be added. Next, examples of the present invention will be shown. Example 1 A photosensitive element for use in a photographic material according to the invention was prepared by sequentially forming the following layers on a transparent base layer consisting of a polyester film. The amount of each substance used below is the amount used per 1 m ² . (1) Mordant layer consisting of 3.6 g of octadecyltrimethylammonium methyl sulfate and 9.0 g of gelatin (2) Reflection layer consisting of 48 g of TiO ₂ and 4.8 g of gelatin (3) Gelatin intermediate layer consisting of 2.6 g of gelatin (4) ) A dye layer containing silver sulfide particles containing 1.25 g of Compound 1 (yellow) and 3.35 g of gelatin (5) Containing a black and white developer, and containing 0.95 g of AgBr, 1.2 g of octadecylhydroquinone sulfonic acid, 0.36 g of octadecyl hydroquinone, and gelatin
Silver bromide emulsion layer (6) containing 2.2 g Protective layer consisting of 2.6 g gelatin After exposure through a stepped wedge, the layer side of the photosensitive element was covered with a polyester film.
A "splittable container" containing an alkaline working fluid having the following composition was used for development of the photosensitive element after imaging exposure had taken place. Sodium hydroxide 25g Phenidone 1g Sodium thiosulfate 2g Sodium sulfite 4g Paraformaldehyde 1g Benzyl alcohol 10ml Hydroxyethyl cellulose (Natrosol
HHK250'') 30g Water Remaining amount 1000ml Add the above image forming composite member (image set) to 1
It was passed between a pair of squeeze rollers, which spread the developer paste between the photosensitive element and the coversheet portion. The thickness of this paste was 140μ. To adjust the thickness of the paste, spacer strips of corresponding thickness were placed laterally along the edges of the image between the photosensitive element and the cover sheet portion. After exposure in the paste for 10 minutes at 20°C, the imaging member was separated and the paste adhering to it was removed. A positive yellow image with good tone was clearly visible to the naked eye through the transparent substrate with _two layers of TiO2 as the background of the image. Example 2 The same procedure as in Example 1 was carried out, but this time the following layers were used in place of layers (4) and (5) described in Example 1. (4) Compound 2 (magenta) 0.83g and gelatin
Dye layer (5) containing silver sulfide particles containing 2.85 g Green sensitized silver bromide emulsion layer containing 0.67 g AgBr, 0.83 g octadecylhydroquinone sulfonic acid, 0.25 g octadecyl hydroquinone and 1.5 g gelatin As in Example 1 After processing according to the standard processing method, a positive magenta dye image was obtained.
Dmin=0.65; Dmax=1.62. Example 3 The same procedure as in Example 1 was carried out, but this time the following layers were used in place of layers (4) and (5) described in Example 1. (4) Compound 3 (cyan) 1.6g and gelatin 2.2g
Red sensitized silver bromide emulsion layer containing 1.65 g of AgBr, 1.2 g of octadecylhydroquinone sulfonic acid, 0.35 g of octadecylhydroquinone and 2.0 g of gelatin as in Example 1. After processing according to the processing method, a positive cyan dye image with good tone was obtained. Example 4 The same operation as in Example 2 was performed, but this time the layer
Compounds 4 and 5 were used in place of compound 2 in (4), respectively. In each case, after processing according to a method similar to that described in Example 1, a positive magenta dye image was obtained. Example 5 The photosensitive material described in Example 2 was processed according to a development method similar to that described in Example 1, but this time, instead of phenidone, the compounds listed in the table below were used as co-developers. Each of these drugs is paste 1
It was used at a rate of 5 g per portion. The results shown in the table below were obtained.

[Table] Example 6 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were formed. (4) Compound 8 (cyano) 1.6g and gelatin 2.2g
(5) a dye layer containing silver sulfide particles containing g; (5) a red sensitized silver bromide emulsion layer containing 1.57 g AgBr, 1.12 g octadecyl hydroquinone sulfonic acid; 0.34 g octadecyl hydroquinone and 1.95 g gelatin; (6) octadecyl hydroquinone sulfonic acid; 1.0
Barrier layer containing silver sulfide particles containing g and 4.0 g of gelatin (7) Compound 7 (magenta) 0.94 g and gelatin
(8) a dye layer containing silver sulfide particles containing 2.85 g; a green sensitized silver bromide emulsion layer (9) containing 1.57 g AgBr, 1.12 g octadecylhydroquinone sulfonic acid, 0.34 g octadecyl hydroquinone and 1.95 g gelatin; Barrier layer similar to (6) (10) 1.48 g of compound 6 (yellow) and 2.85 g of gelatin
(11) A dye layer containing 1.65 g of AgBr, 1.2 g of octadecyl hydroquinone sulfonic acid, 0.35 g of octadecyl hydroquinone and 2.0 g of gelatin (12) A protective layer containing 2.6 g of gelatin. strip,
It was exposed through a color separation wedge and then processed according to a method similar to that described in Example 1. Paste thickness is 260μ
After a development time of 20 minutes, a direct positive pleochroic reproduction (ie, a direct positive pleochroic photograph) of the original (subject) was obtained. Example 7 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were formed. (4) Dye layer containing 1.25 g of Compound 1 (yellow) and 1.35 g of gelatin (5) Silver (silver covering)
Silver chlorobromide (silver chlorobromide) for direct positive use containing 2.0 g of covering) and 1.8 g of gelatin.
(6) A protective layer consisting of 2.6 g of gelatin.A strip of this light-sensitive element was exposed. It was then processed in a manner analogous to that described in Example 1 with the cooperation of the paste bag, cover sheet part and two spacer strips arranged laterally. The thickness of this spacer was 180μ. A paste having the following composition was used as a developer. Potassium hydroxide 25g N,N,N',N'-tetramethyl-p-phenylenediamine 5g Acetyl phenylhydrazine 1g Paraformaldehyde 1g Benzotriazole 0.1g Benzyl alcohol 10ml Hydroxyethyl cellulose (Natrosol)
HHR250'') 35 g water balance 1000 ml After a development time of 10 minutes, a positive yellow dye image with good tone was obtained. Example 8 The same procedure as described in Example 7 was carried out, but this time the following layers were used in place of layers (4) and (5) described in Example 7. (4) Compound 2 (magenta) 0.83g and gelatin
Dye layer (5) containing 1.85 g Green sensitized emulsion layer containing a fog-free direct positive silver chlorobromide emulsion containing 2.0 g silver (silver covering) and 1.8 g gelatin Processing as described in Example 7 After processing according to a similar method, a positive magenta dye image was obtained.
Dmin=0.38; Dmax=1.24. Example 9 The same procedure as in Example 7 was carried out, but this time the following layers were used in place of layers (4) and (5) described in Example 7. (4) Compound 3 (cyan) 1.6g and gelatin 1.2
Dye layer containing g (5) Silver (silver covering 2.0g, gelatin
After processing according to a method similar to that described in Example 7, a positive cyan dye image was obtained. It was done. Example 10 The same operation as in Example 8 was performed, but this time the layer
Compounds 4 and 5 were used in place of compound 3 in (4), respectively. In each case, after processing according to a method similar to that described in Example 7,
A positive magenta image was obtained. Example 11 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were sequentially formed. (4) Compound 8 (cyan) 1.6g and gelatin 2.2g
(5) a red sensitized emulsion layer containing a fog-free direct positive silver chlorobromide emulsion containing 2.0 g of silver (silver covering) and 1.8 g of gelatin (6) octadecylhydroquinone sulfone acid 0.26
Barrier layer (7) with 0.94 g of compound 7 (magenta) and 2.26 g of gelatin
Dye layer (8) containing 2.85 g; Green sensitized emulsion layer (9) containing fog-free direct positive silver chlorobromide containing 2.0 g silver (silver covering) and 1.8 g gelatin; Barrier layer similar to (6) (10) 1.48 g of compound 6 (yellow) and 2.85 g of gelatin
Dye layer containing g (11) Blue sensitized emulsion layer containing a fog-free direct positive silver chlorobromide emulsion containing 2.0 g silver (silver covering) and 1.8 g gelatin (12) 2.6 g gelatin A strip of this imaging member was exposed through a color separation wedge and then processed according to a method similar to that described in Example 7. When the paste thickness was 260μ, a direct positive pleochroic reproduction of the original (ie a pleochroic photograph) was obtained after a development time of 20 minutes. Example 12 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were formed in sequence. (4) Compound 2 (magenta) 0.83g and gelatin
(5) a dye layer containing 2.8 g; a silver bromide emulsion layer containing 1.6 g AgBr and 2.0 g gelatin; (6) a protective layer consisting of 2.6 g gelatin. This photographic material was prepared according to a method similar to that described in Example 1. Exposure and then processing. However, as a developer, a paste having the following composition was used. Sodium hydroxide 25g Benzyl alcohol 10ml Paraformaldehyde 1g Benzotriazole 0.1g Ascorbic acid 0.25g N,N,N',N'-tetramethyl-p-phenylenediamine 5g "Natrosol HHR250" 35g Water Remaining amount 1 Paste thickness was 180μ, a magenta negative reproduction of the original (ie, a negative photograph) was obtained after a development time of 10 minutes. Example 13 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were formed in sequence. (4) Silver sulfide cores, 0.85 g of a known dye-donor compound A as a comparative example (as described in British Patent No. 1405662 and having the structure below) and 2.85 g of gelatin (cyan coating). Dye layer containing dye-donating compound A: (5) Photosensitive layer containing 0.65 g AgBr, 0.84 g octadecyl hydroquinone sulfonic acid, 0.25 g octadecyl hydroquinone and 1.5 g gelatin. (6) Protective coating containing 2.6 g gelatin. A similar material was prepared containing the same amount of compound 28 (invention) instead of compound A in layer (4). In layer (4), the same amount of comparative dye-donor compound B or compound 27 of the invention (yellow coating)
Two other similar materials were produced, including: Dye-donor compound B: Each sheet of material produced above was exposed from behind a gray wedge and developed as in Example 1. The results are shown in Table 1 below. Example 14 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were formed in sequence. (4) a dye layer containing 0.85 g of Compound A (same as that used in Example 13) and 2.85 g of gelatin as a comparative example; (5) a photosensitive layer containing a fog-free direct positive internal image silver halide emulsion; Silver coating 2.1g,
Gelatin coating 1.8g (6) Protective coating of gelatin 2.6g. In layer (4), instead of compound A, the same amount of compound 28 and as a comparative example compound B (same as used in example 13)
or similar materials were prepared containing compound 27, respectively. Exposure and development were carried out as in Example 7. The results are shown in Table 1 below.

[Table] Based on these results, the silver salt diffusion method (Example 13) and the use of reversal emulsion (Example
In 14), it can be seen that the dye-donating compound of the present invention is densitometrically superior to known compounds with a similar structure (higher maximum density, at least partially lower fog density). Example 15 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were formed in sequence. (4) Silver sulfide core and dye-donor compound C as a comparative example (described in British Patent No. 1405662,
(having the structure below) 1.0g and gelatin 1.2
Dye layer containing g dye-donor compound C: (5) Intermediate layer containing 1.3 g of gelatin (6) Photosensitive layer containing 1.37 g of AgBr, 1.0 g of octadecylhydroquinone sulfonic acid, 0.30 g of octadecyl hydroquinone and 1.46 g of gelatin (7) Protective layer containing 1.3 g of gelatin. A similar material was prepared containing the same amount of compound 29 (invention) instead of compound C in layer (4). Exposure and development were carried out as in Example 1. However, the developing paste did not contain benzyl alcohol. The results are shown in Table 2 below. Example 16 Base layer part of Example 1 [transparent base layer and layers (1) and (2)
and (3)], the following layers were sequentially formed. (4) Dye layer containing Compound C (same as that used in Example 15) and 1.2 g of gelatin as a comparative example (5) Photosensitive layer containing non-fogging direct positive internal image silver halide emulsion, 1- (3'-carboxyphenyl)-5-mercaptotetrazole 1 mg,
Octadecylhydroquinone sulfonic acid 0.32g
and silver coating containing 1.57g gelatin
2.0g (6) Protective coating containing 1.3g gelatin. A similar material was prepared containing the same amount of compound 29 instead of compound C in layer (4). Exposure and development were carried out as described in Example 1. However, the viscous developer used had the following composition: KOH 40g Benzyl alcohol 10ml Paraformaldehyde 1g Benzotriazole 3g Ascorbic acid 0.25g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 1.3g Acetyl phenylhydrazine 1.0g Hydroxyethyl cellulose 35g Add water to make 1000ml. The thickness of this paste was 180 μm. The results are shown in Table 2 below. Example 17 Base layer part described in Example 1 [transparent base layer and layer
(1), (2) and (3)], the following layers were sequentially formed. (4) Dye layer containing 0.8 g of dye-donating compound D (having the following structural formula) and 0.8 g of gelatin as a comparative example Dye-donating compound D: (5) Photosensitive layer containing a non-fogging direct positive silver chloride-bromide-iodide emulsion, 1 mg of 1-(3'-carboxyphenyl)-5-mercaptotetrazole;
Octadecylhydroquinone sulfonic acid 0.12g
and silver coating 2.8 containing 2.3 g gelatin
g (6) Octadecylhydroquinone sulfonic acid 0.27
(7) A hardened layer containing 0.2 g of a carbodiimide type instant hardening agent. A similar material was prepared containing the same amount of Compound 38 instead of Compound D in layer (4). Exposure and development were carried out as described in Example 16. However, the developer composition did not contain the fogging agent acetophenylhydrazine. The results are shown in Table 2.

Table Example 18 A photosensitive element of a color photographic material for dye diffusion transfer was prepared by applying the following layers on a polyethylene coated paper layer support: (1) Dye containing 0.67 g of compound 39 and 1.2 g of gelatin. Layer (2) Photosensitive silver chloride-bromide emulsion containing 2.3 g of gelatin (applied amount of silver 0.44 g) (3) Layer (4) containing 0.85 g of gelatin and 0.2 g of 2-acetyl-5-octadecyl-hydroquinone 4 - Hardening layer comprising 0.06 g of β-sulfoethyl-N-morpholinocarbonylpyridinium betaine and 0.6 g of gelatin. Image-receiving elements were also prepared by applying the following layers to a polyethylene-coated paper layer support: (1) from 4,4'-diphenylmethane diisocyanate and N-ethyldiethanolamine;
Mordant layer (2) comprising 2.3 g of a polymeric mordant which is a polyurethane quaternized with epichlorohydrin and 5 g of gelatin; Hardened layer comprising 0.36 g of 4-β-sulfoethyl-N-morpholinocarbonyl-pyridinium betaine and 0.7 g of gelatin. After exposure of the photosensitive element, the photosensitive element and the image-receiving element were immersed in a developer of the following composition: Cyclohexanol 10 g Na ₂ SO ₃ 2 g KBr 3 g 5-methylbenzotriazole 1 g KOH 40 g 4-hydroxymethyl-4-methyl -1-Phenyl-3-pyrazolidinone 8g Make up to 1000ml with water. Both the photosensitive element and the image receiving element were pressed together with their coating layers facing each other and held there for 2 minutes. After separation, the receiver element was rinsed and dried. A negative magenta dye image was obtained:
Dmin 0.16; Dmax 1.42.

Claims (1)

[Scope of Claims] 1 Consists of at least one photosensitive silver halide emulsion layer, and associated therewith, a layer of the following formula: _{In the formula , _} is hydrogen, an alkyl group, an aryl group, an acyl group or a heterocyclic group, and these alkyl, aryl, acyl and heterocyclic groups taken together with one of the substituents R ₂ and R ₃ 5- containing at least one nitrogen atom
or may complete a 6-membered heterocyclic ring; R ₂ represents hydrogen, an alkyl group, an aryl group, or a heterocyclic group, and these alkyl groups, aryl groups, and heterocyclic groups are substituted. Together with one of the groups R ₁ and R ₃ they may complete a 5- or 6-membered carbocyclic or heterocyclic ring, or R ₂ carries two substituents. represents nitrogen, the first substituent of which is a group selected from the group consisting of hydrogen, alkyl, aryl and acyl groups, which alkyl, aryl and acyl groups together with R ₁ represent at least It may complete a 5- or 6-membered heterocyclic ring containing one nitrogen atom, and the second substituent together with hydrogen and R ₃ contains at least one nitrogen atom. is a group selected from the group consisting of groups completing a 5- or 6-membered heterocyclic ring containing R ₃ , provided that the two substituents on the nitrogen atom are not both jointly hydrogen; represents a group _which together with one of the substituents R ₁ and R ₂ completes _{a 5-} or 6-membered carbocyclic or heterocyclic ring; at least 1
A heterocyclic or carbocyclic ring completed by one or two of these substituents is one having a ballast group; provided that R ₂ together with R ₃ forms an aromatic carbocyclic ring. If it completes the formula ring, R ₁ is −
A non-diffusible dye-donor compound represented by OR ₄ and the carbocyclic ring having a hydrogen atom or a group other than a hydroxy or amino group or a derivative thereof in the para-position relative to R ₁ and the non-diffusible dye-donor compound is one that can be oxidized by the oxidation products of the silver halide developer and, when oxidized, decomposes by the alkali of the developer to form the formula X-SO ₂ -NH _2. A color photographic material capable of releasing a diffusible dye represented by the following formula, wherein X has the above meaning. 2 The non-diffusible dye-donating compound has the following formula () _{In the formula , _} represents hydrogen, an alkyl group, an aryl group, an acyl group or a heterocyclic group, and these alkyl groups, aryl groups, acyl groups and heterocyclic groups together with the substituent R ₆ contain at least one nitrogen atom. It may complete a 5- or 6-membered heterocyclic ring comprising;
R ₆ represents an aryl group or an acyl group, and these aryl and acyl groups may be combined with R ₁ to complete a 5- or 6-membered heterocyclic ring; R ₇ is an alkyl group. represents a group, an alkoxy group, an acylamino group or an arylamino group; the heterocyclic ring completed by at least one of the substituents R ₆ and R ₇ or R ₁ and R ₆ has a ballast group; A color photographic material according to claim 1 or 1, which has the following. 3. The color photographic material according to claim 2, wherein the substituents R ₁ and R ₆ complete a benzimidazoline ring or a quinazoline ring. 4 The non-diffusible dye-donating compound has the following formula () In the formula, X represents a dye or dye precursor group; _R2 represents hydrogen, an alkyl group, an aryl group, or a heterocyclic group; _R8 represents an alkyl group, an alkoxy group, a halogen group, a sulfo group, a sulfamyl group; represents one or more substituents selected from the group consisting of a group (one or two of the hydrogen atoms on the nitrogen atom of this group may be substituted with an alkyl group or an aryl group): The color photographic material according to claim 1, wherein at least one of the substituents R ₂ and R ₈ has a ballast group. 5. Color photographic material according to any one of claims 1 to 4, further comprising an image-receiving element suitable for forming a dye image by imagewise transfer of a diffusible dye. .