JPS5945139B2 - Color photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photosensitive material, and more particularly to a color photosensitive material containing a compound that releases a diffusible dye through a redox reaction associated with development of silver halide.

JP-A-48-33826 describes a color diffusion transfer color image forming method using such a dye-releasing redox compound.

The dye-releasing redox compounds mentioned here are:
p-, in which the dye moiety and the non-diffusible phenol moiety or naphthol moiety are bonded at the p-position via a sulfonamide group;
It is a sulfonamide phenol or p--sulfonamide naphthol compound. When exposed in the coexistence with a photosensitive silver halide emulsion, the dye-releasing redox compound is oxidized depending on the amount of developed silver halide, and this is oxidized by the alkaline processing solution to the dye part having a sulfonamide group and non-diffusion. The dye portion of the former is transferred to an image-receiving element to form a transferred image. In the case of the former, that is, p-sulfonamidophenol, according to additional tests by the present inventors, it is difficult to provide sufficient transfer density, and in the latter, p-naphthoquinone remains after the dye is released, resulting in a yellow stain. Even if the transferred image can be used, it is difficult to use the photosensitive layer side unit as a negative or positive image even if desilvering treatment is performed.

A diffusion transfer color image forming method using a dye-releasing redox compound having 0-sulfonamidophenol as a redox center is described in JP-A-51-113624.

Here, specific examples of dye-releasing redox compounds include 2-sulfonamide 4-hexadecyloxy-5-methylphenol and 2-sulfonamide 4-hexadecyloxy-5-methylphenol.
A method using hexadecyloxy-5,6,7,8-tetrahydro-1-naphthol and the like has been described.

Redox compounds with 0-sulfonamidophenol as the redox center are superior in providing relatively high transfer density, but they are susceptible to (1) dye transfer in unexposed areas and (2) oxidation due to redox reactions. Further improvements are desired in terms of the efficiency with which the oxidized redox compound releases dye (ie, the efficiency of dye transfer).

An object of the present invention is to provide a silver halide photographic material containing an improved dye-releasing redox compound.

Specifically, the first objective is to provide a photosensitive material containing a dye-releasing redox compound that provides a higher transfer density when used in a diffusion transfer method. Second, the residual color after dye release (
An object of the present invention is to provide a photosensitive material containing a dye-releasing redox compound that provides a residual dye image (in a photosensitive element) with less residual dye (stain). Third, it is an object of the present invention to provide a photosensitive material containing a dye-releasing redox compound with suppressed so-called Dmin, which does not cause dye transfer in unexposed areas. The present inventors have discovered that a photosensitive material containing a compound represented by the following general formula satisfies the above objectives.

Here, G is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis, COI is a dye or a group that gives a dye, R is an alkyl or aromatic group, and X is a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group, or an alkylthio group. represents a group, and X<15R may be connected to form a ring.

The alkyl groups and alkyl residues mentioned above include unsubstituted and substituted alkyl groups as well as straight chain, branched and cyclic alkyl groups.

In particular, in the above, specific examples of G include acyloxy groups such as acetoxyl group and propionyloxy group in addition to hydroxyl group.

As G, a hydroxyl group is particularly preferable. Examples of CO1 include groups such as azo dyes, azomethine dyes, indoaniline dyes, indophenol dyes, triphenylmethane dyes, anthraquinone dyes, indigo dyes, and metal complex salts thereof. Typical examples of the group that gives a dye represented by CO2 include those that give a dye by hydrolysis, such as those described in JP-A-48-125818, U.S. Pat. Nos. 3,222.196 and 3,307,947, etc. Examples include acylated auxochromes of dyes (temporary short-wave dyes) as described in . By temporarily shortening dye absorption during exposure through acylation, it is possible to prevent desensitization due to light absorption when these color image forming agents are mixed with light-sensitive emulsions and coated. can. Note that for this purpose, it is also possible to use a dye that has different hues when transferred onto the mordant and when present in the emulsion layer. Note that the COll moiety can have a group that imparts water solubility, such as a carboxyl group or a sulfonamide group. Preferred examples of R include linear or branched alkyl groups having 1 to 30 carbon atoms (e.g. methyl, ethyl, propyl, butyl, bentyl, hexyl, octyl, dodecyl, pentadecyl, hexadecyl, octadecyl, isopropyl, isobutyl, t-butyl, t-amyl, neopentyl, etc.)
Examples include substituted alkyl groups (eg, hydroxyethyl, benzyl, methoxyethyl, etc.), phenyl groups, and substituted phenyl groups (eg, p-amylaminophenyl, p-nitrophenyl, etc.).

Preferred examples of Straight chain or branched alkyl group;
Substituted alkyl groups such as hydroxylethyl, benzyl, phenylethyl, methoxyethyl, ethoxyethyl; phenyl group; substituted phenyl groups; methoxy, ethoxy, propyloxy, isopropyloxy, octyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyl Straight chain or branched alkyloxy groups such as oxy; phenyloxy groups; substituted phenyloxy groups; substituted alkyloxy groups; halogen atoms such as chlorine and bromine; acylamino groups such as acetylaminolistearylamino; methylthio, ethylthio, octylthio, dodecylthio , an alkylthio group such as hexadecylthio; and the like, and X and 0R may form a fused ring. In order to prevent these compounds from being diffused or washed out as they are by the alkali used during the development of the light-sensitive material, they require a ballast group that substantially prevents them from being diffused or washed out.

The size or number of carbon atoms required for the ballast group depends on the conditions used, such as treatment time, alkali concentration,
Although it varies depending on the number and type of water-soluble groups in the COl moiety, at least 8 or more in total including X(!:1R) is required. However, in principle there is no upper limit to the number of carbon atoms.Generally, the total number of carbon atoms in XI::.R is 1.
The most preferred range is around 3 to 40. research
ResearchDi-SclOsu
RE) magazine No. 13024 ('75) describes o-sulfonamide phenols, and among them, 2-sulfonamide phenol having an alkyl group at the 5-position has almost no development activity and is therefore not suitable for dyes. However, it is clear that the attachment of the OR group at the 4-position of the phenol in the compounds of the present invention makes a significant difference.

Furthermore, the fact that the compound of the present invention has a benzonorbornene skeleton produces an important difference in performance.

This effect is explained by Arnold et al. T. ArnOld et al. J.
AmerChemSOc63l3l7 (248)) and Castro et al. (R.O. CastrOetalHelr.
Chim. The Mils-Nixon effect (Mils-NixOn effect) as described by Acta3l536 (゛48))
It can be inferred by analogy whether the change in the redox potential caused by the effect) is simply due to ring distortion, which increases the rate of hydrolysis of the oxidized quinoneimide, or whether side reactions are suppressed by the bridgehead hydrogen atom. It is not beyond the scope of. This compound is o-
Quinoneimide is produced, which undergoes hydrolysis and leaves the sulfonamide moiety, but the resulting o-benzoquinone has only a hypochromic absorption compared to the naphthoquinones mentioned above. It is thought that this reduces the residual color after release. In the most preferred embodiment of the invention, G is a hydroxyl group, X is a hydrogen atom, and R is a dodecyl, tetradecyl, hexadecyl or octadecyl group.

The dye-releasing redox compounds used in the present invention are illustrated below. Compound 1 When processing the light-sensitive material of the present invention, it is desirable to carry out the processing in the presence of an auxiliary developer in order to facilitate the redox reaction.

The following can be exemplified as the auxiliary developer that can be used. 1-phenyl-3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1
-Phenyl-4-methyl-3-pyrazolidone p-aminophenol N-methyl-p-aminophenol N,N-diethylaminophenol p-tolylhydroquinone N,N-diethyl-p-phenylenediamine 6-hydroxy-1 , 2,3,4-tetrahydroquinoline The dye-releasing redox compound of the present invention is dispersed in a hydrophilic colloid carrier in a conventional manner.

In the present invention, in particular, a combination of a blue-sensitive silver halide emulsion and a yellow dye-releasing redox compound, a combination of a green-sensitive emulsion and a magenta dye-releasing redox compound, and a combination of a red-sensitive emulsion and a cyan dye-releasing redox compound. Photosensitive materials are useful. The combined units of these emulsions and dye-releasing redox compounds may be coated in layers in a face-to-face relationship in the light-sensitive material, or the redox compound may be mixed in the emulsion in the form of particles and coated as a single layer. may be done. In a preferred multilayer structure, a blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion are sequentially arranged from the exposure side.
The dye-releasing redox compound of this invention is used in an amount such that the molar ratio of silver to dye-releasing redox compound in the silver halide emulsion with which it is combined is in the range of about 50-0.5, preferably about 10-2.

The silver halide emulsion used in the light-sensitive material of the present invention is preferably an internal latent image type emulsion that can directly form a positive silver image when combined with a fogging agent in order to obtain a transferred positive color image. Also, the photosensitive element of the present invention (including a redox compound and a photosensitive layer)
, a film unit in which an image receiving element (including a mordant layer) and a processing element (a container containing a processing liquid) are integrated.

Details of such a film unit can be found in U.S. Pat. No. 4,055.
It is described in many documents such as 5,428. The redox compounds of this invention generally have an azo dye sulfonyl chloride and various organic ballast groups.

- It can be synthesized by reacting with an aminophenol derivative. Furthermore, methods for synthesizing dye moieties and their sulfonyl chlorides are described in JP-A-48-12581;
No. 48-33826, No. 49-114424, No. 4
No. 9-126332. Next, some specific synthesis examples and examples from among the compound examples related to the present invention will be described below.

Synthesis Example Synthesis of Compound 8 a) 6-acetyl-1,4-methano-1,2.3,4
-Synthesis of tetrahydro-5,8-naphthalenediol 1
,4-methano-1,2,3,4-tetrahydro5,8
-Naphthalene diol 52f! was heated and dissolved in 300 ml of acetic acid.

Boron trifluoride (BF3) was added to this at 80 to 90° C. for about 1.5 hours with stirring, and the O reaction solution was poured into ice water in Step 21. The precipitated crystals were filtered out and thoroughly washed with water.

The crystals were treated with a 2N caustic soda aqueous solution 500a and then acidified with hydrochloric acid. The precipitated crystals were collected and washed with water.
Yield 40f! (65%) b) 6-acetyl-1,4-
Synthesis of methano-1,2,3,4-tetrahydro-5,8-naphthalenediol-oxime The ketone 389 obtained in the above ω was heated and dissolved in 200 d of ethanol, and to this was added ice-free sodium 399 and hydroxylamine hydrochloride 1
A solution of 89 dissolved in 200 d of water was added and refluxed for about 1 hour.

The reaction solution was poured into ice water, left overnight, and then collected. Yield 24
V (60%) c) 5-hydroxy-2-methyl-6,9-methano-6,7,8,9-tetrahydro-naphtho[2.1-d]
Synthesis of oxazole (b) above? The obtained oxime 109 was dissolved in 80 d of acetic acid, and while refluxing, dry hydrogen chloride gas was introduced for 2 hours.

After the reaction was completed, the reaction solution was poured into ice water, and the precipitated crystals were filtered out and washed with water. Yield 89 (87%) d) 5-hexadecyloxy-2-methyl-6,9-methano-6,7,8,9-tetrahydronaphtho[2,1-
d]-Synthesis of oxazole 6.7 g of oxazole obtained in the above c) was dissolved in 70 ml of dimethylformamide, and further 89 ml of anhydrous potassium carbonate and 1 ml of hexadecyl bromide were added.
1f! was added and stirring was continued at 80 to 90°C for 3 hours.

After removing the inorganic substances, 150 d of methanol was added to the bottom liquid and cooled on ice. The precipitated crystals were collected. Yield 11.6f!
(85%) e) Synthesis of 6-amino-8-hexadecyloxy-5-hydroxy 1,2,3,4-tetrahydronaphthalene hydrochloride Oxazole obtained in the above φ9.
7 g was refluxed for 4 hours with 50 d of ethanol and 40 d of concentrated hydrochloric acid.

After the reaction was completed, the mixture was cooled on ice to precipitate crystals. The crystals were collected and washed with water. Yield 9.59 (95%) f) Synthesis of Compound Example 8 O-aminophenol hydrochloride obtained in e) above 8.8
9 was reacted with the following dye, sulfonyl chloride 129, in a mixture of dimethylacetamide 70 and pyridine 5.

After about 1 hour, the reaction was completed, and the reaction solution was poured into ice water containing hydrochloric acid to collect the precipitated crystals. The crystals were dissolved in benzene-acetone (4:1 volume ratio) and subjected to silica gel chromatography using this as a developing solvent. The pure title compound eluted as expected. Yield 6.5g (
33%) Example 1 A photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support.

(1) A layer containing the following magenta DRR compound (0.999/I) (tricyclohexyl phosphate (0.19 g/I) and gelatin (2.0 f!/I).

(Support) Green-sensitive internal latent image type direct reversal silver bromide emulsion (silver content 1.75g/I), gelatin 1.8f1/I), the following nucleating agent (0.06W/I), and A layer containing sodium pentadecylhydroquinone sulfonate (0.11 f!/a).

(3) A layer containing gelatin (1.1y/y).

A treatment liquid having the following composition was filled into a 0.89 rupturable container. In the characteristic curve obtained using the processing solution direct inversion emulsion, Dmin+
The following mordant (3,09/Tr
A mordant layer sheet containing 1) and gelatin (3.09/I) was prepared.

The sample containing the magenta DRR compound in layer (1) of the photosensitive sheet is referred to as (A), and the sample containing the magenta DRR compound 14 [magenta D
RBA compound] (1.04V/I)
B) was produced.

After exposing samples (A) and (B), they were integrated with a container containing the processing solution and a mordant layer sheet, and heated at 15°C and 2°C.
The treatment liquid was spread to a thickness of 80 fim0) using a pressing member at 5°C.

After 5 minutes, the mordant layer sheet was peeled off and immersed in a 2% acetic acid solution, then washed with water and dried to obtain a transferred color image.

The results are shown in Table 1. The larger the value (÷), the higher the contrast.

As is clear from Table 1, compared to sample (A), sample (B) has a higher maximum transmission density, a lower minimum transmission density, and provides characteristic values with good sharpness of the toe gradation. Ta.

Claims (1)

[Scope of Claims] 1. A color photographic material containing a dye-releasing redox compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (here G
is a hydroxyl group, or a group that provides a hydroxyl group by hydrolysis,
Col is a dye or a group that provides a dye, R is an alkyl or aromatic group, X is a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group, or an alkylthio group; It may be formed.