JPH0352850B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photographic material for color diffusion transfer using a surface latent image type emulsion. (Prior art) In general, photographic light-sensitive materials for color diffusion transfer method use a type that uses a surface latent image type emulsion as a silver halide emulsion and a type that uses a direct positive emulsion (direct reversal emulsion) (for example, Japanese Patent Application Laid-Open No. 55-21067 No.) is known. A surface latent image type emulsion mainly forms a latent image on the surface of silver halide grains, and is usually called a "negative emulsion." On the other hand, direct positive emulsion forms a positive silver image by exposing a positive subject, but unlike negative emulsion, it directly forms a positive silver image without requiring reversal processing or other reversal mechanism. It is an emulsion, and in that sense it is completely different from a surface latent image type emulsion (or a negative type emulsion) in terms of photographic chemistry. Color image formation methods based on color diffusion transfer methods also include
There are various different image forming mechanisms, but a redox compound (hereinafter referred to as a "colorant") that releases a diffusible dye through a redox reaction following development of silver halide (this compound itself is an alkaline It is important to use methods that take advantage of the immobility under certain conditions. In order to obtain a direct reversal color image with a negative coloring material that releases a diffusible dye upon silver development of a silver halide emulsion, it is necessary to combine it with a direct positive emulsion, but the development speed is usually faster than that of a negative emulsion. This results in drawbacks such as slowness. Positive-tone colorants, in which the release of diffusible dyes from the combined colorants is suppressed during development of a light-sensitive silver halide emulsion, are contrasted to surface latent image-type (negative-tone) silver halide emulsions. It can be combined with emulsions and can be expected to produce color diffusion transfer positive photographs with quick image completion. As a positive coloring material, for example, JP-A-49-
111628, 51-63618, 52-4819, 53-
110827, 53-110828, 54-130927, 56-
There are compounds disclosed in No. 164342 and No. 57-119345. Among these, coloring materials (BEND compounds) that are immobile even under alkaline conditions described in JP-A-53-110827 and JP-A-53-110828, or JP-A-54-
130927, 56-164342, and 57-119345, the colorant (Carquin compound) that is immobile even under alkaline conditions is a compound that releases a diffusible dye by accepting at least one electron, It is usually used in combination with an electron donating compound ( _ED ). In order to obtain a reversal color image (positive image) by combining the above-mentioned positive coloring material and a surface latent image type (negative type) silver halide emulsion, development is performed under highly alkaline conditions. Silver fog (fog in silver halide development) tends to increase, resulting in a decrease in the maximum image density (Dmax) of the reversal color image. In the color diffusion transfer method using a surface latent image type silver halide emulsion, it was reported in Japanese Patent Application Laid-Open No. 57 (1982) that certain mercapto compounds are used to prevent silver fog.
-Known from No. 168249. This compound has the following general formula; (wherein X represents a nonmetallic atom necessary to form the nucleus that completes the 5- or 6-membered heterocyclic group of the above structure, and R is H, an alkali metal, or a group that can be cleaved in the aqueous alkaline treatment composition. and R ₁ has a pKa value of about 7 to about 14 that can be anionized, and - the silver salt of the mercaptan that forms from the splitting or ionization of BR is aqueous alkaline within the PH range where R ₁ ionizes to an anion. represents a group or its precursor group that is more soluble in the processing composition below this pH range than the silver salt in question is)
Among them, R ₁ in the formula can be ionized into an anion, and the pKa value in the ionized state is about 7 to 14. However, when this compound is used, a decrease in sensitivity occurs, or even if the silver fog decreases, the development speed of silver halide decreases significantly, resulting in photographs with soft gradation even if Dmax is high, or photographs with extreme In this case, only photos with high minimum image density (Dmin) can be obtained. (Objects of the Invention) The first object of the invention is to provide a photographic material for color diffusion transfer method which produces color transfer images with high sensitivity, high Dmax and high contrast. The second object is to provide a color diffusion transfer method (color image forming method) that suppresses silver fog without reducing sensitivity or slowing down development speed (without softening tone). (Structure of the Invention) As a result of intensive studies, the present inventors have found that at least one surface latent image type photosensitive silver halide emulsion layer is provided on the support, and the relationship is combined with the silver halide emulsion layer. A light-sensitive material for color diffusion transfer method containing an immobile dye-providing compound that releases a diffusible dye as a result of development under alkaline conditions, and which is represented by the following general formula () or (). It has been found that the above object can be effectively achieved by a photographic material for color diffusion transfer, which is characterized in that it is processed in the presence of at least one type of mercapto compound or its precursor. general formula [In the formula, X is

[Formula] is a divalent group represented by -S- or -O-; R ₁ is a hydrogen atom, an alkali metal ion, a quaternary ammonium ion, a quaternary phosphonium ion, or an organic group that can be split in an alkaline processing solution. ; L is an arylene group or an alkylene group; R ₂ is -SO ₃ or -CO ₂ in the alkaline processing solution
is a group that produces a group; R ₃ is a halogen atom, a carboxyl group, a sulfo group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, an aryl group, a substituted aryl group, or

[Formula] (R ₄ and R ₅ may be the same or different, each being a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, or a substituted aryl group)
represents; n represents an integer from 0 to 2; ] Incidentally, in the mercapto compound of the present invention represented by the general formula () or (), R ₂ in the general formula is -SO ₃ group or -
One of its characteristics is that it is a group that can generate a COO group, and the pKa values of the generated -SO ₃ group and -COO are both 6 or less. On the other hand, the mercapto compound of JP-A-57-168249 cited in the explanation of the prior art is characterized by the pKa of its anion group being 7 to 14, and is therefore clearly different from the compound of the present invention. It is something. The present inventors have surprisingly discovered that the lower pKa value of the anion group generated from R ₂ is 6 or less, the better the silver fog suppression effect, even though it does not delay development and has a small decrease in sensitivity. They found an effect. Such a fact could not have been predicted from the conventional technology. (Detailed explanation of the structure of the invention) R ₂ in the general formulas () and () is a dissociated -SO ₃ group or -CO ₂ by dissociation or decomposition reaction under alkaline conditions based on the treatment liquid.
A group that produces a group, and specific examples thereof include the non-dissociable acid type group of the above-mentioned dissociative group (-SO ₃ H, -CO ₂ H),
Its alkali metal salt groups (−SO ₃ Li, −SO ₃ Na, −
SO ₃ K, −CO ₂ Li, −CO ₂ Na, −SO ₃ K, etc.).
In addition, quaternary ammonium ions (NH ₄ ⁺ ,
N(CH ₃ ) ⁺ ₄ , N(C ₂ H ₅ ) ₄ ⁺ , etc.) or quaternary phosphonium ions (P ⁺ (C ₆ H ₅ ) ₄ , etc.).
Further, ester derivative groups of both groups and aliphatic alcohol or aromatic alcohol (e.g. -CO ₂ C ₆ H ₅ ,
_-CO2C2H5 , _{-CO2C6H4NO2 , etc.} ) _, amide groups ( _{e.g. -CONH2 , -CONHCH3 , -CONHC6H5 )} ,
A group in which a group decomposable under alkaline conditions such as an addition derivative group with an electron-deficient olefin (for example, -CH ₂ CH ₂ CN) is bonded to both groups is also effective as R ₂ . Preferred R ₂ for use in the present invention include:
The above-mentioned non-dissociated acid type groups, alkali metal salts thereof, and esters thereof are included, and the most preferred are the non-dissociated acid type groups or their alkali metal salts. As X in general formula (), -NH- and -S-
is particularly preferred.

[Formula] is preferably

【formula】 or

[Formula] (m is an integer from 0 to 8). There are no particular restrictions on the types of substituents for the substituted alkyl group, substituted alkoxy group, substituted aryl group, and substituted aralkyl group constituting R ₃ as long as they do not impair the effects of the present invention. For example, substitution of the alkyl group or aryl group Substituents commonly known as groups (e.g. halogen atoms, alkyl groups, aryl groups,
(amino group, substituted amino group, carboxyl group, sulfo group, etc.) can be applied. On the other hand, R ₁ in general formulas () and () is a hydrogen atom, an alkali metal ion, a quaternary ammonium ion, a quaternary phosphonium ion, or U.S. Pat.
Protecting groups described in JP-A-57-135949 and the like are effective. Specific examples of the alkali metal ion, quaternary ammonium ion, and quaternary phosphonium ion are those listed above for _R2 .
In a particularly preferred embodiment of the invention, R ₁ is a hydrogen atom or an alkali metal ion. The compound of general formula () or () of the present invention can be added to a silver halide emulsion layer or a layer superimposed thereon, to a processing solution, or to a cover sheet. Although various methods of addition are possible, it is particularly preferable to add the compound of general formula () or () of the present invention to the silver halide emulsion layer. The amount of the compound of general formula () or () added is not particularly limited, but is preferably about 0.001 mol% to 5 mol%, more preferably 0.01 mol% to 5 mol%, based on the number of moles of silver in each silver halide emulsion layer. 2 mol%
It is. When the compound of the present invention is added to a layer other than the silver halide emulsion layer, or when added to a processing solution, it is added in an amount corresponding to the above-mentioned amount. When adding the compound of general formula () or () of the present invention to a silver halide emulsion layer, various known methods can be adopted, but it is possible to gradually add it to the emulsion coating solution as a water or alcohol solution. Alternatively, depending on the compound, it may be added as an emulsion obtained by emulsifying and dispersing it using an auxiliary solvent and gelatin. In particular, the former method is generally simple. One of the great advantages of the present invention is that the present invention has made it possible to effectively suppress silver halide without adversely affecting the development speed and sensitivity of silver halide, and thus it has become possible to employ various development acceleration methods. It is one.
That is, as is well known, development accelerators have generally been difficult to use because of their general tendency to increase fogging silver. However, with the effective silver fog suppressing means of the present invention, the generation of silver fog can be significantly suppressed even when a development accelerating means is provided, and as a result, it is possible to obtain a diffusion transfer photosensitive material that can complete an image very quickly. It became. It is also possible to use known development accelerators in the present invention, and specific examples thereof include alcohols represented by benzyl alcohol, amino alcohols such as aminopentanol, quaternary ammonium salts, and thioethers. and hydroquinones. Preferred specific examples of the compounds used in the present invention are listed below. The compounds of the present invention can generally be synthesized by using the methods described in the following documents. British Patent No. 1275701, US Patent No. 3266897, R.
G. Dubenko; VDPanchenko; Khim.
Geterotsikl.Soedin, Sb-1, Azoto oder
zhaschie Geterotsikly1967, pp. 199-201,
Brit No. 1275701, JP-A No. 111846-1983, JP-A-55
-21067, JP-A-50-89034, JP-A-53-28426
issue. The surface latent image type (negative type) silver halide emulsion used in the present invention is a hydrophilic colloidal emulsion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof. The dispersion can have various halide compositions, but silver bromide, silver iodobromide or silver chloroiodobromide with an iodide content of 10 mole % or less and a chloride content of 30 mole % or less are particularly preferred. The silver halide emulsions used in the present invention can have color sensitivity expanded by spectral sensitizing dyes, if desired.
As the spectral sensitizing dye, cyanine dyes, merocyanine dyes, etc. can be used as appropriate. Among the above-mentioned silver halide emulsions, high-speed negative emulsions are particularly useful in the present invention, and any conventionally known high-speed negative emulsions can be used. These negative emulsions are Research Disclosure No.
22534 (1983), West German patent application (OLS) 3241642A1
Emulsions containing silver halide grains of tabular grains as described in et al. are also suitably used. As mentioned above, surface latent image type emulsions significantly increase fogging silver in the diffusion transfer system, so it is thought that the effects of the present invention are particularly noticeable. In addition, this study found for the first time that the difference in development speed between exposed areas (where silver deposition is greatest) and non-exposed areas (where silver deposition is least) is small for surface latent image type emulsions. It has been found that it is more effective to incorporate the compound of the invention in advance into the silver halide emulsion layer or a layer near it. Among these, it is preferably contained in a red-sensitive emulsion layer (particularly an emulsion imparted with red sensitivity by a trimethine-based cyanine sensitizing dye) or its vicinity. An immobile dye dye-donor compound (colorant) that releases a diffusible dye (including its precursor) as a result of development under alkaline conditions is a dye developer that becomes diffusible under alkaline conditions. are clearly distinguishable. The above-mentioned coloring material that can be used in the present invention may be a negative-working coloring material or a positive-working coloring material, but it is said that it creates a positive reversal dye image. For our purposes, the latter is preferable. Typical negative colorants are N-substituted sulfonamide redox compounds that release dyes upon oxidation and subsequent hydrolysis. On the other hand, as examples of positive coloring materials that can be used in the present invention, US Pat.
No. 4199354, No. 4199355, No. 4371604, JP-A-Sho
No. 49-111628, No. 51-63618, No. 52-4819,
No. 53-69033, No. 54-130927, No. 57-119345
Examples include compounds having a positive redox core as described in Japanese Patent Application No. 58-60289. In particular, positive coloring materials suitably used in the present invention include:
It is an immobile colorant that emits a diffusible dye by accepting at least one electron, and this compound is often used in combination with a diffusion-resistant electron donating compound (hereinafter referred to as "ED compound"). The ED compound is a strongly reducing compound or its precursor present in the emulsion layer or a layer adjacent to the emulsion layer, and specific examples include, for example, U.S. Pat.
It is described in No. 4263393, JP-A-56-138736, etc. Containing such an ED compound in the emulsion layer or its vicinity is also a cause of increasing the silver fog in the silver halide emulsion, and the present invention is further effective in suppressing the silver fog caused by this ED. Shows remarkable effects. Naturally, coloring materials and
Even if a coloring material with an integrated ED compound, that is, a coloring material with an ED function in the same molecule, was used, the same effect was obtained in terms of increasing fogging silver. Among these, particularly preferable specific compounds include those having the following structures, but the present invention is of course not limited to these coloring materials. Further, a type having a positive redox core and an ED compound built into the same molecule is also suitable. The dyes formed from the colorants used in this invention may be ready-made dyes or alternatively dye precursors that can be converted into dyes in photographic processing steps or additional processing steps, with the final image dye being a metallic dye. It may or may not be standardized. Representative dye structures useful in the present invention include azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, metalized and unmetallized dyes. Among these, azo-based cyan, magenta and yellow dyes are particularly important. Next, in order to give examples of the dye moieties used in the present invention, we will include specific examples as negative-tone coloring materials, but these dye moieties can be combined with positive-tone redox cores as long as the connecting part is changed. Can be easily used as a positive coloring material. Specific examples of yellow colorants are given in Japanese Patent Publication No. 49-2618;
U.S. Patent No. 3309199, Japanese Patent Publication No. 57-12140, Japanese Patent Publication No.
No. 51-114930, No. 54-111344, No. 56-16130,
No. 56-71072, No. 54-79031, No. 53-64036 and No. 54-23527;
4148643; Research Disclosure 17630 (1978),
No. 16475 (1977). Also, a specific example of the magenta coloring material is shown in a US patent.
No. 3453107, Japanese Patent Publication No. 43950 (1973), and Japanese Patent Publication No. 1973 (1977)
106727; U.S. Patent No. 3932380, U.S. Patent No. 3931144, U.S. Pat.
No. 3932308, Japanese Patent Publication No. 50-115528, No. 52-106727
No. 53-23628, No. 54-65034, No. 55-
No. 36804, No. 54-161332, No. 55-4028, No. 56
-73057, 56-71060, 55-134, 53-
35533, U.S. Patent No. 4207104, U.S. Patent No. 4287292, U.S. Pat.
4357410 and 4357412. Furthermore, a specific example of the same cyan coloring material is
-32130, JP-A-52-8827, JP-A-49-126331,
No. 51-109928, No. 54-99431, No. 53-149328
No. 52-8827, No. 53-47823, No. 53-
No. 143323, No. 54-99431, No. 56-71061, No. 53
-64035 and 54-121125, U.S. Patent No. 4142891,
No. 4195994, No. 4147544, No. 4148642, European Patent No. 53037, No. 53040; Research
Disclosure No. 17630 (1978) and Disclosure No. 16475 (1977)
It is stated in the number. Further, as a type of dye precursor, a dye-releasing redox compound having a dye moiety whose light absorption is temporarily shifted in the photosensitive element can also be used in this patent; issue,
No. 55-53329, U.S. Patent No. 3336287, U.S. Patent No. 3579334
No. 3982946 and British Patent No. 1467317. As the developer used in the present invention, any silver halide developer can be used as long as cross-oxidation occurs with the desired compound (coloring material, ED compound, etc.). Such a developer may be included in the alkaline processing composition or in an appropriate layer of the light-sensitive material. Examples of developing agents that can be used in the present invention are as follows. Hydroquinones described in JP-A-56-16131;
Aminophenols, phenylenediamines, pyrazolidinones [e.g. phenidone, 1-m-tolyl-4-hydroxymethyl-4-methyl-3-
Pyrazolidinone, dimezone, 1-p-tolyl-
4,4-dihydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-(4'-methoxyphenyl)-4-methyl-4-hydroxymethyl- 3-pyrazolidinone, 1-phenyl-4-
methyl-4-hydroxymethyl-3-pyrazolidinone] and the like. Of these, black and white developers (among them pyrazolidinones) are particularly preferred, as they generally have properties that reduce stain formation in the image-receiving layer more than color developers such as phenylene diamines. The processing composition used to process the photographic material of the present invention preferably contains a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium phosphate and has a pH of about 9 or more.
Preferably with an alkaline strength of 11.5 or higher, the treatment composition comprises sodium sulfate, ascorbate,
Antioxidants such as piperidinohexose retactone may be included, and silver ion concentration regulators such as potassium bromide may also be included. It may also contain viscosity increasing compounds such as hydroxyethyl cellulose and sodium carboxymethyl cellulose. The alkaline processing composition may also contain a compound, such as benzyl alcohol, which has the effect of promoting development or promoting dye diffusion. When the photosensitive material of the present invention constitutes at least a part of a film unit consisting of a photosensitive element, an image receiving element (these elements may be integrated), a processing element (processing composition), and optionally a cover sheet, The treatment composition is described in U.S. Pat. No. 2,543,181;
No. 2643886, No. 2653732, No. 2723051, No.
It is preferable to use the container by filling it into a pressure-rupturable container such as those described in Japanese Patent Application No. 3056491, Japanese Patent No. 3056492, Japanese Patent No. 3152515, and the like. To reproduce natural colors by the subtractive color method, a photosensitive material is used that consists of at least two combinations: an emulsion that has selective spectral sensitivity in a certain wavelength range and a coloring material that has selective spectral absorption in the same wavelength range. Ru. In particular, light-sensitive materials consisting of a combination of a blue-sensitive silver halide emulsion and a yellow dye coloring material, a combination of a green-sensitive emulsion and a magenta coloring material, and a combination of a red-sensitive emulsion and a cyan coloring material are useful. These combination units of emulsion and coloring material may be coated in layers in a face-to-face relationship in a light-sensitive material, or in the form of individual grains (coloring material and silver halide grains are present in the same grain).
may be formed into a single layer, mixed and applied as a single layer. Scavengeers for oxidized developers can be used in various intermediate layers of the light-sensitive materials of the invention. Suitable materials are described in Research Disclosure, Vol. 151 (November 1976), pp. 76-79. Between the intermediate layer and the layer containing the coloring material, there is a
A separation layer may be provided as described in No. 52056. Furthermore, a silver halide emulsion may be added to the intermediate layer as described in JP-A-56-67850. Regarding the mordant layer, neutralization layer, neutralization speed control layer (timing layer), etc. that can be used in the light-sensitive material for the color diffusion transfer method of the present invention, for example, US Pat. No. 4,268,625
The items listed in the item are applicable. Color photographs can be obtained using the photosensitive material of the present invention through the following steps. That is, the photosensitive material (or photosensitive element) is exposed imagewise. The exposed silver halide emulsion is then developed by treatment with an alkaline processing composition in the presence of a developer (electron transfer agent) and the mercapto compound (or derivative thereof) of the present invention. Development of the silver halide emulsion then results in the formation of an image-forming distribution of diffusible dye, which then diffuses (transfers) at least a portion of this dye into the image-receiving layer (or image-receiving element). This results in a diffusion-transferred color image on the image-receiving layer. Furthermore, by the same method as above, color photographs can also be obtained by utilizing the dyes remaining in the light-sensitive material (or light-sensitive element). As described above, the light-sensitive material of the present invention primarily consists of a light-sensitive element (1) in which at least one silver halide emulsion layer is coated on a support.
The present invention also includes embodiments in which the image-receiving element (or image-receiving layer) (2) is combined. A photosensitive material (ie, a film unit) comprising (1), (2), and (3) in addition to a means for supplying processing composition (3) is also included within the scope of the present invention. In the embodiments including (1), (2), and (3) above, the container for supplying the treatment composition contains the contents (treatment composition).
is arranged, for example, to be provided between the photosensitive layer and the cover sheet, or between the photosensitive layer and the image-receiving layer. The image-receiving element described above may be placed on a separate support so that it is superimposed with the light-sensitive element after exposure.
Such embodiments are described, for example, in US Pat. No. 3,362,819. Alternatively, the image-receiving element may be superimposed with the photosensitive element throughout before, during and after exposure. Alternatively, the image receiving element may be provided on the same support as the photosensitive element. Such an integrated configuration (film unit) is described, for example, in Belgian patent 757,960, and a variant thereof in Belgian patent 575,959. According to this embodiment, the support is transparent;
On top of this, at least an image receiving layer, a light reflecting layer (white layer),
A light-blocking layer, a photosensitive element is coated thereon, and a rupturable container containing an alkaline processing composition and a light-blocking agent is coated with a top layer (protective layer) of the photosensitive element and a transparent cover sheet (coated with a neutralizing layer and a timing layer). are located between the This film unit is loaded into a camera, exposed through a transparent cover sheet, and then passed between a pair of pressure members in the camera when the film unit is taken out. A pressure member ruptures the container to spread the processing composition and light shielding agent onto the photosensitive element of the film unit. each silver halide emulsion is developed by a processing composition;
As a result, the formed diffusible dye diffuses into the image-receiving layer in an image-like manner, and a transferred image is obtained there. In this way, a color photograph can be viewed against the background of the light-reflecting layer (white layer). Furthermore, as a variant of integral construction, a release layer may be provided between the image-receiving layer and the photosensitive element. Thereby, after forming the transferred image, the photographer can peel it off as needed and use it as a normal color print or color slide. Example 1 A laminated integrated color diffusion transfer photosensitive sheet, a cover sheet, and a processing solution were prepared as follows. Preparation of photosensitive sheet On a polyethylene terephthalate transparent support,
Photosensitive sheets 1 to 9 were prepared by applying each layer in the following order. (1) Copoly [styrene-N-vinylbenzyl-N
-Methyl-piperidinium chloride〕3.0
g/m ² , an image-receiving layer containing 3.0 g/m ² of gelatin. (2) Titanium dioxide 20g/m ² , gelatin 2.0g/m ²
A white reflective layer containing. (3) Carbon black 2.0g/ ^m2 and gelatin 1.0
A light shielding layer containing g/m ² . (4) The following cyan coloring material 2×10 ^-4 mol/m ² , the following cyan coloring material
ED compound A2×10 ⁻⁴ mol/m ² , N,N-diethyl laurylamide 0.1 g/m ² and gelatin 0.8
layer containing g/m ² . (5) Red-sensitive surface latent image type silver bromide emulsion (silver content 0.6
g/m ² ), 0.02 mol/mol of the compounds shown in Table 1
Ag, N,N-diethyl laurylamide 0.01
g/m ² and a layer containing 0.6 g/m ² of gelatin. (6) A layer containing 0.5 g/m ² of 2,5-di-t-pentadecylhydroquinone and 0.4 g/m ² of gelatin. (7) Magenta coloring material with the following structure 3×10 ^-4 mol/m ² ,
The following ED compound A3×10 ^-4 mol/m ² , N, N-
Layer containing 0.1 g/m ² of diethyl laurylamide and 0.8 g/m ² of gelatin. (8) Green-sensitive surface latent image type silver bromide emulsion (silver 0.6g/
m ² ), 0.01 mol/mol Ag of the compound shown in Table 1,
N,N-diethyl laurylamide 0.01g/m ² ,
and a layer containing 0.6 g/m ² of gelatin. (9) Same as layer (6). (10) Yellow coloring material with the following structure 4×10 ^-4 mol/m ² ED compound A4×10 ^-4 mol/m ² below, N,N-diethyl laurylamide 0.1 g/m ² and gelatin
A layer containing 0.8 g/m ² . (11) Blue-sensitive surface latent image type silver bromide emulsion (silver 0.6g/
m ² ), compound 0.005mol/mol Ag shown in Table 1,
N,N-diethyl laurylamide 0.01g/m ² ,
Layer containing 0.8 g/m ² of gelatin. (12) 4x each of the UV absorbers with the following structures.
10 ^-4 mol/m ² , Tris(2-ethylhexyl)
Phosphate (0.02g/m ² ) and gelatin
UV absorbing layer containing 0.30g/ ^m2 . (13) Protective layer containing polymethyl methacrylate latex (average particle size 4 μ, 0.10 g/m ² ), gelatin (0.15 g/m ² ) and triacryloyltriazine (0.02 g/m ² ) as hardener. Structure of Cover Sheet A cover sheet was prepared by sequentially coating the following layers (1') to (3') on a transparent polyethylene terephthalate support. (1′) 80 pairs of acrylic acid and butyl acrylate
20 (weight ratio) copolymer (22 g/m ² ) and 1,4-bis(2,3-epoxypropoxy)-butane (0.44 g/m ² ). (2') Acetyl cellulose (100 g of acetyl cellulose is hydrolyzed to produce 39.4 g of acetyl groups) (3.8 g/m ² ) and 60:40 (weight ratio) of styrene and maleic anhydride.
methanol-opened product (0.23 g/m ² ) of copolymer (molecular weight approximately 50,000) and 5-(2-cyano-1-methylethylthio)-1-phenyltetrazole (0.154 g/m ² ). Containing layer. (3') Styrene-n-butyl acrylate-
49.7:42, 3:3:5 (weight ratio) copolymer latex of acrylic acid-N-methylol acrylamide and 93 of methyl methacrylate-acrylic acid-N-methylol acrylamide.
A 2μ thick layer coated with a 4:3 (weight ratio) copolymer latex mixed at a solid content ratio of 6:4. Composition of treatment liquid 1-p-tolyl-4-hydroxymethyl-4
-Methyl-3-pyrazolidone 10g Methylhydroquinone 0.3g 5-methylbenzotriazole 3.5g Sodium sulfite (anhydrous) 0.2g Carboxymethylcellulose Na salt 58g Potassium hydroxide (28% aqueous solution) 200cc. Benzyl alcohol 1.5cc Carbon black 150g Water 685c.c.

[Table] As is clear from Table 1, although conventional photosensitive sheets 2 to 4 have a silver fog suppression effect (Dmax up), there is a large decrease in sensitivity (see shadow - sensitivity value) and a large development speed. decrease (softening, i.e. γ
However, the photosensitive sheet of the present invention has an excellent property of effectively suppressing silver fog without substantially causing a decrease in sensitivity and without delaying the development speed (no softening of tone). I understand. Example 2 In order to confirm the improvement effect of the present invention, the following photosensitive element and image receiving element were prepared. Photosensitive sheet A photosensitive sheet was prepared by coating each layer on a polyethylene terephthalate transparent support as follows. Back side: (a) Light shielding layer containing 4.0 g/m ² of carbon black and 2.0 g/m ² of gelatin. Emulsion layer side: (1) The following cyan colorant 2×10 ^-4 mol/
m ² , ED compound used in Example 1
A layer containing A2×10 ⁻⁴ mol/m ² , N,N-diethyl laurylamide 0.1 g/m ² , and gelatin 1 g/m ² . (2) Red-sensitive surface latent image type silver chloroiodobromide emulsion (Cl:Br:I=20:75:5), the amount of silver was 1 g/m ² , the compounds shown in Table 2 were added in the amounts shown in Table 2, and gelatin 1
emulsion layer containing g/m ² . (3) Layer containing 1 g/m ² of 2,5-di-tert-pentadecylhydroquinone and 0.5 g/m ² of gelatin. (4) Layer containing 0.2 g/m ² of gelatin. Receiving element paper support: 150μ thick paper laminated with 30μ polyethylene on each side. Titanium oxide is dispersed and added to the polyethylene on the image-receiving layer side in an amount of 10% by weight based on the polyethylene. Back side: (a) Light shielding layer of carbon black 4.0g/m ² and gelatin 2.0g/m ² . (b) Titanium oxide 8.0g/m ² , gelatin
1.0g/ ^m2 white layer. (c) Protective layer of gelatin 0.6 g/m ² . Image-receiving layer side: (1) Acrylic acid with an average molecular weight of 50,000
Butyl acrylate (molar ratio 8:
2) Neutralizing layer containing 22 g/m ² of copolymer. (2) Cellulose acetate with an acetylation degree of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of sample) and an average molecular weight of about 10,000.
Neutralized timing layer containing 4.5 g/m ² of styrene-maleic anhydride (1:1 molar ratio) copolymer in a weight ratio of 95:5. (3) Styrene-butyl acrylate-
Acrylic acid-N methylol acrylamide weight ratio 49.7/42.3/4/4
A polymer latex emulsion polymerized with a weight ratio of 93 to 3 to 4 and a polymer latex emulsion polymerized with a weight ratio of methyl methacrylate/acrylic acid/N-methylol acrylamide in a weight ratio of 93 to 3 to 4 so that the solid content ratio is 6 to 4. layer with a total solids content of 1.6 g/m ² . (4) 3.0g/m ² of the following polymer and gelatin
3.0g/ ^m2 with coating aid Image-receiving layer coated using (5) Protective layer coated with gelatin 0.6g/ ^m2 . Treatment liquid [1-p-tolyl-4-hydroxymethyl-4
-Methyl-3-pyrazolidone 6.9g Methylhydroquinone 0.3g 5-methylbenzotriazole 3.5g Sodium sulfite (anhydrous) 0.2g Carboxymethylcellulose/Na salt 58g Potassium hydroxide (28% aqueous solution) 200c.c. Benzyl alcohol 1.5cc Water 835c .c.] After exposing the photosensitive sheet to light through a color test chart, the cover sheet was placed on top of the other, and the following processing solution was spread between both sheets to a thickness of 85 μm (spreading was done with the help of a pressure roller). ). The processing was carried out at 25°C, and the photosensitive sheet and image-receiving sheet were peeled off 90 seconds after the processing. Table 2 shows the results of measuring the reflection density of the image receiving sheet.

【table】

[Table] As is clear from Table 2, in the light-sensitive material using Comparative Compound E, when a large amount is added, Dmax increases, but the sensitivity decreases significantly, whereas in the light-sensitive material of the present invention, the amount of Dmax is sufficiently high. It can be seen that even with the addition of , there is almost no decrease in sensitivity, and no softening of contrast is observed (in fact, there is an increase in contrast), which is an extremely excellent photographic material.

Claims (1)

[Scope of Claims] 1. An alkaline compound having at least one surface latent image type (negative type) photosensitive silver halide emulsion layer on a support and in combination with the silver halide emulsion layer. A light-sensitive material for color diffusion transfer method containing an immobile dye-providing compound that releases a diffusible dye as a result of development under the following conditions, and further comprising a mercapto compound or A photographic light-sensitive material for color diffusion transfer method, characterized in that it is processed in the presence of at least one kind of its precursor. general formula In the formula, _X is a divalent group represented by -S- or -O-; is an organic group that can be split with; L is an arylene group or an alkylene group; R ₂ is -SO ₃ or -CO ₂ in the alkaline processing solution.
R ₃ is a halogen atom, carboxyl group, sulfo group, alkyl group, substituted alkyl group, alkoxy group, substituted alkoxy group, aryl group, substituted aryl group, or [Formula] (R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, or a substituted aryl group; n is an integer of 0 to 2; represent