A silver halide light-sensitive photographic material

Description

[0001] The present invention relates to a silver halide light-sensitive photographic material, more specifically to a silver halide light-sensitive photographic material for photodisplay application which suits rapid processing and has good sharpness.

[0002] A typical display method with a color photograph in such locations as department stores, restaurants, hotel lobbies and subway platforms is a "transmittance system (back-light system) where an image formed on a support is displayed by light illuminated from the back of the image; this system is known to provide vivid image in a specific environment such as dark room or the outdoors at night.

[0003] Since the image is displayed by transmitted light in this system, the photographic material employed requires higher image density than that of ordinary color paper. As a result, such a material inevitably requires much increased coating amounts of silver halide and coupler than ordinary color paper, which results in requiring as double processing time as ordinary color paper and therefore, makes it necessary to process the photographic material more rapidly.

[0004] Configuration, size and composition of silver halide grains in a silver halide emulsion for a photographic material greatly affect a developing speed, and especially the composition of halide most significantly affects it; it is well known that silver halide of high chloride content can notably accelerate developing.

[0005] A dye is added to a hydrophilic colloid layer in order to absorb light of a specific wavelength for controlling a sensitivity of a photographic emulsion. Also, a dye is added to inhibit halation or irradiation for improving sharpness of a photographic material.

[0006] The dyes used for these applications are requested to have prescribed spectral absorption characteristics for the respective applications; to be thoroughly decolored, readily eluted from a photographic material and thereby prevent stain on the material after processing; to exert no adverse effects to a photographic emulsion such as sensitization, desensitization and fogging; and to have good stability in a coating solution and a photographic material.

[0007] The photographic material for display is requested to more strictly satisfy the above requirements since it contains a larger amount of dye in order to attain higher sharpness.

[0008] Many dyes have been so far proposed to satisfy the above requirements, such as oxonol dyes disclosed in U.S. Patent Nos. 506,385 and 3,247,127 and Japanese Patent Examined Publication 13168/1968; stylyl dyes disclosed in U.S. Patent No. 1,845,404; merocyanine dyes disclosed in U.S. Patent Nos. 2,493,747, 3,148,187 and 3,282,699; cyanine dyes disclosed in U.S. Patent No. 2,843,486; and anthraquinone dyes disclosed in U.S. Patent No. 2,865,752.

[0009] Among these dyes, oxonol dyes having two pyrazolone skeletons have been used as a useful dye that least adversely affect a photographic emulsion since they are decolored in a processing solution and readily eluted from a photographic material.

[0010] Many of these oxonol dyes cause no problems as far as a silver halide emulsion in a photographic material contains higher silver bromide. However, it was found that they often cause problems against a silver halide emulsion having a higher silver chloride content, such as sensitization to an undesirable spectral range, increased fog, and larger sensitivity fluctuation due to temperature or humidity change.

[0011] The sensitization to an undesirable spectral range is liable to result in worse image quality because of color imbalance in a printing process. Fog is caused most likely by an eluted or decolored dye or its decomposed product activated in a processing solution. The larger sensitivity fluctuation by temperature or humidity variation results in lack of stable image quality depending on storage conditions such as temperature/humidity at a laboratory.

[0012] These are the specific problems where a silver halide emulsion of higher silver chloride content is used. However, the silver halide emulsion of higher AgCℓ content is necessary for rapid processing and therefore, there is required a photographic material containing such emulsion and capable of stably providing good image quality even in a rapid processing.

[0013] EP-A-0362734, which is an earlier document according to Article 54(3) EPC, describes photographic materials having an opaque polyethylene-laminated paper support, at least one emulsion layer containing grains having a silver chloride content of not less than 90 mole % and at least one layer containing an oxonol dye. The background art discussed therein describes different types of dyes for light sensitive materials.

[0014] The object of the present invention is to provide a rapidly processable silver halide light-sensitive photographic material containing a dye that is inert in an emulsion and capable of providing an image of high sharpness.

[0015] This object is attained by a backlighting type silver halide light-sensitive photographic material for photodisplay having on one side of a polyester film support at least one silver halide emulsion layer, wherein the silver halide emulsion layer contains silver halide grains of 80 mole% or more silver chloride accounting for not less than 80 mole% of total grains contained in the layer and a compound represented by following Formula I:

wherein R₁ to R₆ independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group and a heterocyclic group, provided that one of R₁ and R₂ and one of R₃ and R₄ each represent the groups other than a hydrogen atom and that at least one of R₁ to R₆ has a water-solubilizing group or a substituent having a water-solubilizing group; L₁ to L₅ independently represent a methine group; and m and n independently represent 0 or 1.

[0016] At least one of the silver halide emulsion layers constituting the silver halide light-sensitive photographic material of the invention contains silver halide grains having 80 mole% or more silver chloride content.

[0017] The photographic material comprises preferably a plurality ot silver halide emulsion layers of different spectral sensitivities each having a 80 mole% or more silver chloride content.

[0018] In the invention, the silver halide grains comprise silver chloride of 99.9 to 99.5 mole%, preferably 99.8 to 99.9 mole%, silver bromide of 0.1 to 1.5 mole%, preferably 0.2 to 1.0 mole%, and silver iodide of 0 to 0.02 mole, preferably 0 mole%.

[0019] The silver halide grains may be mixed with silver halide grains of different compositions.

[0020] The silver halide grains of the high chloride content share not less than 80 mole%, preferably not less than 90 mole% in the total silver halide grains contained in the same layer.

[0021] The size of the silver halide grains used for the invention is preferably 0.1 to 1.5 µm, more preferably 0.3 to 1.0 µm. The grain size can be measured by conventional methods used in the art.

[0022] The size distribution of the silver halide grains may be either polydispersed or monodispersed. The monodispersed silver halide grains are preferable, in which a variation coefficient is not more than 0.22, preferably not more than 0.15.

[0023] The silver halide grains can be prepared by the ammonia method, and neutral or the acid method. The silver salts and halides solutions are added by the double-jet method, and single-jet method, the reverse-precipitation method, and the conversion method. The silver halide grains prepared by the neutral method or the acid method are preferable since they are highly sensitive while they have low fog and excellent pressure resistance and safelight property.

[0024] Silver salt and silver halide solutions are added preferably by the double-jet method, more preferably by the pAg-controlled double jet-method, wherein pAg is controlled in the range of 3 to 9.

[0025] The silver halide grains of high chloride content used for the invention may be either a surface latent image type or an internal latent image type.

[0026] The silver halide grains contain preferably 0.1 to 1.5 mole% of silver bromide. This silver bromide may be added at any step during formation of the silver halide grains and desalination, and during or after chemical ripening.

[0027] If bromide is incorporated into the photographic material after the desalination, it may be simply added in the form of water-soluble bromide, or by adding water soluble bromide and water soluble silver salt simultaneously or separately.

[0028] A necessary amount of silver bromide may be added in several steps; for example, in two steps, during and after the desalination. In the invention, it is added preferably during desalination.

[0029] Bromide may be localized either on the surface or inside of the grains, or otherwise, uniformly distributed from the core to the surface of the grains.

[0030] Unnecessary salts may be removed from the emulsion preferably after the formation of the grains, and the emulsion may be subjected to chemical ripening and then to conventional chemical sensitization with sulfur compounds.

[0031] In addition to the above chemical sensitization, the silver halide grains may be also subjected to noble metal sensitization, sulfur sensitization with active gelatin, selenium sensitization and reduction sensitization.

[0032] The silver halide grains may be sensitized by various sensitizing dyes in order to provide the grains with a sensitivity to a prescribed spectral range.

[0033] The preferred sensitizing dyes are cyanine dyes, merocyanine dyes and complex cyanine dyes.

[0034] The compound represented by Formula I may be added to the photographic component layers including other silver halide emulsion layers and non-light-sensitive layers such as an intermediate layer, a protective layer, a filter layer, and an antihalation layer as well as the emulsion layers containing the AgX grains of high AgCℓ content.

wherein R₁ to R₆ independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and a heterocyclic group, provided that R₁ and R₂, or R₃ and R₄ are not simultaneously a hydrogen atom and that at least one of R₁ through R₆ contains a water solubilizing group or a substituent having a water solubilizing group.

[0035] The alkyl groups represented by R₁ through R₆ are methyl, ethyl, propyl, isopropyl, butyl and t-butyl, each of which may have a substituent such as a hydroxy group, a sulfo group, a carboxyl group, a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

[0036] The aryl groups represented by R₁ through R₆ are phenyl, 2-methoxyphenyl, 4-nitrophenyl, 3-chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-methanesulfonylphenyl, 4-sulfophenyl, 3-sulfophenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2-chloro-5-sulfophenyl, 2-methoxy-5-sulfophenyl, 2-hydroxy-4-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 2,6-diethyl-4-sufophenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 2,4-disulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 4-carboxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 3,6-disulfo-α-naphthyl, 8-hydroxy-3,6-disulfo-α-naphthyl, 5-hydroxy-7-sulfo-β-naphthyl, and 6,8-disulfo-β-naphthyl.

[0037] The alkenyl groups represented by R₁ through R₆ are vinyl and allyl.

[0038] The heterocyclic groups represented by R₁ through R₆ are a pyridyl group such as 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-sulfo-pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2-pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, and 3-nitro-2-pyridyl; an oxazolyl group such as 5-sulfo-2-benzooxazolyl, 2-benzooxazolyl, and 2-oxazolyl, a thiazolyl group (e.g. 5-sulfo-2-benzothiazolyl, 2-benzothiazolyl, and 2-thiazolyl); an imidazolyl group such as 1-methyl-2-imidazolyl and 1-methyl-5-sulfo-2-benzoimidazolyl; furyl group such as 3-furyl; a pyrrolyl group such as 3-pyrrolyl; a thienyl group such as 2-thienyl; a pyrazinyl group such as 2-pyrazinyl); a pyrimidinyl group such as 2-pyrimidinyl and 4-chloro-2-pyrimidinyl), a pyridazinyl group such as 2-pyridazinyl; a purinyl group such as 8-purinyl; an isooxazolynyl group such as 3-isooxazolynyl; a selenazolyl group such as 5-sulfo-2-selenazolyl; a sulfolanyl group such as 3-sulfolanyl; a piperidinyl group such as 1-methyl-3-piperidinyl; a pyrazolyl group such as 3-pyrazolyl, and a tetrazolyl group such as 1-pyrazolyl. Additionally, R₁ and R₂, or R₃ and R₄ may form a ring such as piperazyl group, a piperidyl group, and a morpholyl group.

[0039] The preferred groups represented by R₅ and R₆ are an alkyl group, an aryl group, and a heterocyclic group, more preferably, an alkyl group and an aryl or heterocyclic group that has at least one water-solubilizing group, and, most preferably an alkyl group.

[0040] The water-solubilizing groups are a sulfo group or its salt, a carboxyl group or its salt, a hydroxy group, a sulfate ester group, a phosphynyl group, a phosphono group, and a phospholyl group.

[0041] Typical examples of the dye represented by Formula I are shown below:

[0042] These dyes of the invention are readily synthesized by the method described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent 0.P.I. Publication) No. 143342/1983. A 3-carboxy-5-pyrazolone derivative, which is a starting material in this synthesis, is synthesized by the methods described in Japanese Patent O.P.I. Publication No. 185934/1988, Journal of the American Chemical Society 71, 983 (1949), and Chem. Ber. 109, 253 (1976). Typical synthesis schemes are as follows.

[0043] In these schemes, R¹, R and R³ independently represent an alkyl group, an alkenyl group, an aryl group and a heterocyclic group; R and R³ are preferably alkyl groups.

[0044] The photographic material used in the invention may contain the dye represented by Formula I in the silver halide emulsion layers as an antiirradiation dye, or in the non-light sensitive hydrophilic colloid layers as a filter dye or an antihalation dye.

[0045] It is preferable that the compound defined by m=0 and n=0 in Formula I is present in a blue-sensitive silver halide emulsion layer; the compound defined by m=1 and n=0, in a green-sensitive silver halide emulsion layer; the compound defined by m=1 and n=1, in a red-sensitive silver halide emulsion layer.

[0046] Two or more dyes may be used together, or in combination with other types of dyes. The dye is usually incorporated into the photographic component layers by dissolving it in water or organic solvent such as alcohol, glycol, cellosolve, dimethylformaldehyde, dibutylphthalate and tricresylphosphate, if necessary, emulsifying, and then adding to a coating solution.

[0047] An addition amount of the dye is 0.01 to 10 mg/dm, preferably, 0.03 to 5.0 mg/dm.

[0048] The support used in the invention is preferably transparent or translucent. A translucent support containing white pigment is preferably used.

[0049] The useful white pigments are inorganic and organic ones, preferably an inorganic white pigment including sulfate salts of alkali earth metals such as barium sulfate; carbonate salts of alkali earth metals such as calcium carbonate; silicas such as fine powder silica and synthetic silica; calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, and clay. Barium sulfate, calcium carbonate and titanium oxide are preferable, and barium sulfate and titanium oxide are more preferable.

[0050] The white pigment is added in an amount of 5 to 50 wt%.

[0051] A support of the invention is arbitrarily selected from those having an oxygen permeation rate of not more than 2.0 mℓ/m.hr.atm. The support has preferably the oxygen permeation rate of not more than 1.0 mℓ/m.hr.atm, and a plastic film can satisfy this requirement. The oxygen permeation rate is measured by a known method such as that specified in ASTM D-1434 Recommended Practice. This measurement method is also applicable to the present invention.

[0052] The polymers for the support used in the invention are polyesters such as polyethyleneterephthalate. The oxygen permeation rate of the polyesters is independent of humidity and, therefore it has the same oxygen permeation rate in a humid atmosphere as in a dry atmosphere.

[0053] The thickness of the support is 150 to 250 µm, preferably 160 to 200 µm.

[0054] Any polyester film support may be used as a transparent support in the invention as far as it is virtually transparent. The particularly preferable is polyethylene terephthalate film.

[0055] In the invention, there may be provided on the side opposite to the side of an emulsion layer, an antihalation layer containing a material capable of absorbing light. This material has a function to prevent halation on the support by absorbing the light transmitted from the emulsion layers.

[0056] The light-absorbing material is selected from various inorganic materials and dyes having this action.

[0057] Example of the inorganic material is colloidal metal. Examples of the organic material for this purpose are dyes coupled with polymers for fixation (so-called mordant dye) so that the dye is not eluted into a color developer.

[0058] Examples of the inorganic light-absorbing materials are colloidal silver and colloidal manganese, preferably colloidal silver.

[0059] The aromatic primary amine color developing agents used for a color developer are aminophenol derivatives and p-phenylenediamine derivatives. These compounds are used in an amount of 0.1 to 30 g, preferably 1 to 15 g per 1ℓ of a color developer.

[0060] The color developer may contain various conventional additives in addition to the above color developing agent.

[0061] The pH level of the color developer is usually 7 or higher, preferably 10 to 13. The color developing temperature is usually 15°C or higher, preferably 20 to 50°C. For rapid processing, the developing temperature is preferably 30°C or higher.

[0062] Color developing time is usually 10 minutes or shorter, preferably 2 minutes 30 seconds or shorter, and more preferably 30 seconds to 2 minutes.

[0063] The photographic material is subjected to bleaching after color developing, and then to fixing. Bleaching and fixing may be carried out simultaneously in the same bath.

EXAMPLES

[0064] The invention is described hereunder by referring to the examples.

Example 1

[0065] Sample No. 1 was prepared by coating the respective coating solutions as shown in Table 1 on a translucent support made of 180 µm-thick transparent polyethylene terephthalate film containing barium sulfate of 10 g/m.

[0066] The added amounts in the table are represented in g/m, and the amounts of silver halide emulsion and colloidal silver are values converted to silver.

[0067] The photographic material Sample Nos. 2 through 37 were prepared in the manner identical to Sample No. 1 except that the emulsions in Layers 1, 3 and 5 were replaced with following EM-A, EM-B and EM-C, respectively and that the dyes added to Layers 1, 3 and 6 were varied as shown in Tables 2-1 and 2-2. In Sample No. 6, there was used the same AgX emulsion of a low AgCℓ content as in Sample No. 1. The amount of the dye of the invention added to Layer 1 was 0.005 g/dm.

[0068] Each sample was exposed by a normal method, and was subjected to developing according to processings A and B.

Preparation of blue-sensitive silver halide emulsion

[0069] Solutions A and B were added to 1000 mℓ of a 2% aqueous gelatin solution at 40°C in 30 minutes according to the double-jet method while keeping pAg at 6.5 and pH at 3.0, and then Solutions C and B were added in 180 minutes according to the double jet method while keeping pAg at 7.3 and pH at 5.5.

[0070] pAg was controlled by the method described in Japanese Patent O.P.I. Publication No. 45437-1984, while pH was controlled with an aqueous solution of sulfuric acid or sodium hydroxide.
Solution A




Solution B

AgNO₃	10 g
Water to make	200 mℓ

Solution C

NaCℓ	102.7 g
KBr	1.0 g
Water to make	600 mℓ

Solution D

AgNO₃	300 g
Water to make	600 mℓ

[0071] After completion of addition, desalination was performed using 5% aqueous solution of Demol N (Kao Atlas) and a 20% aqueous solution of magnesium sulfate. Then, the mixture was blended with an aqueous gelatin solution to prepare monodispersed emulsion EM-1 containing AgX grains having an average grain size of 0.85 µm, a variation coefficient (σ/

) of 0.07, and a silver chloride content of 99.5 mole%.

[0072] EM-1 was chemically sensitized in 90 minutes at 50°C using the compounds specified below to prepare a blue-sensitive silver halide emulsion EM-A.

Preparation of green-sensitive silver halide emulsion

[0073] There was prepared in the manner identical to that of EM-1, monodispersed emulsion EM-2 containing AgX grains having an average grain size of 0.43 µm, a variation coefficient (σ/

) of 0.08 and a silver chloride content of 99.5 mole%, except that the time for adding Solutions A and B and Solutions C and D was changed.

[0074] EM-2 was chemically sensitized in 120 minutes at 55°C using the compounds specified below to prepare a green-sensitive silver halide emulsion EM-B.

Sodium thiosulfate	1.5 mg/mole AgX
Chloroauric acid	1.0 mg/mole AgX
Stabilizer SB-5	6 x 10⁻⁴ mole/mole AgX
Sensitizing dye D-2	4.0 x 10⁻⁴ mole/mole AgX

Preparation of red-sensitive silver halide emulsion

[0075] There was prepared in the manner identical to that of EM-1, monodispersed emulsion EM-3 containing AgX grains having an average grain size of 0.50 µm, a variation coefficient (σ/

) of 0.08 and a silver chloride content of 99.5 mole%, except that the time for adding Solutions A and B and Solutions C and D was changed.

[0076] EM-3 was chemically sensitized in 90 minutes at 60°C using the compounds specified below to prepare a red-sensitive silver halide emulsion EM-C.

Sodium thiosulfate	1.8 mg/mole AgX
Chloroauric acid	2.0 mg/mole AgX
Stabilizer SB-5	6 x 10⁻⁴ mole/mole AgX
Sensitizing dye D-3	8.0 x 10⁻⁵ mole/mole AgX

D-1 (blue-sensitive emulsion layer)

D-2 (green-sensitive emulsion layer)

D-3 (red-sensitive emulsion layer)

Processing A	Temperature	Time
Color developing	35.0 ± 0.3°C	45 sec.
Bleach-fixing	35.0 ± 0.5°C	45 sec.
Stabilizing	30 - 34°C	90 sec.
Drying	60 - 80°C	60 sec.

Color developer

[0077] 

[0078] Water was added to a total of 1ℓ, and the pH was adjusted to 10.10.

Bleach-fixer

[0079] 

Ferric ammonium ethylenediaminetetraacetate dihydrate	60 g
Ethylenediaminetetraacetate	3 g
Ammonium thiosulfate (70% aqueous solution)	100 mℓ
Ammonium sulfite (40% aqueous solution)	27.5 mℓ

[0080] Water was added to a total of 1ℓ, and the pH was adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizer

[0081] 

5-chloro-2-methyl-4-isothiazoline-3-one	1.0 g
Ethylene glycol	1.0 g
1-hydroxyethylidene-1,1-diphosphonic acid	2.0 g
Ethylenediaminetetraacetic acid	1.0 g
Ammonium hydroxide (20% aqueous solution)	3.0 g
Ammonium sulfite	3.0 g
Fluorescent brightening agent (4,4'-diaminostylbene disulfonate derivative)	1.5 g

[0082] Water was added to a total of 1ℓ, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Processing B

[0083] This processing is identical to Processing A except that processing time was varied to 90 seconds for color developing, 90 seconds for bleach-fixing, 180 seconds for stabilizing, and 120 seconds for drying.

[0084] The samples were evaluated for the characteristic values as follows.

(1) Sensitometry

[0085] Each of the processed samples was evaluated for sensitivity, gradation and maximum density (Dmax) with the PDA-65 photographic densitometer (Konica Corporation). The sensitivity is a value relative to that of Sample No. 2 processed with Processing B, which is set at 100.

(2) Fog

[0086] Each sample was subjected to both of the above processings, and its transmittance density was evaluated with Model 310 TR of X Right Company.

(3) Sharpness

[0087] Each sample was exposed to red light through a resolution test chart and then subjected to the above processing. The density of a cyan image was measured with a microphotometer, and the sharpness was calculated from the following equation:

The larger this value is, the higher the sharpness is. The results are summarized in Tables 2-1 and 2-2.

[0088] As can be understood from the results in Tables 2-1 and 2-2, Sample No. 1 (Comparison) containing the AgX emulsions of low silver chloride content exhibited insufficient sensitivity and maximum density (Dmax) even where it was treated in double processing time. In Sample No. 6 containing the same emulsion and the dyes of the invention, the sharpness was improved while the sensitivity and Dmax were not yet improved.

[0089] Sample Nos. 2, 3, 4 and 5 (Comparison) containing the comparative dyes and the AgX emulsions of high AgCℓ content exhibited insufficient sharpness while sensitivity and Dmax were improved.

[0090] Sample Nos. 7 through 37 (Invention) containing the AgX emulsions of high AgCℓ content and the dyes of the invention apparently exhibited improvement in all of the sensitometry, fogging and sharpness.

Example 2

[0091] Example 1 was repeated to prepare Samples No. 38 to 73 except that the support was replaced by a 180 µm-thick transparent polyethylene terephthalate film.

[0092] Each sample was exposed, processed and evaluated in the same manners as in Example 1.

[0093] The results are summarized in Tables 3-1 and 3-2.

[0094] It is apparent from the results in Tables 3-1 and 3-2 that the effects of the invention can be attained with the transparent polyethylene terephthalate film support.

Example 3

[0095] Examples 1 and 2 were repeated except that in Sample Nos. 7 through 37 and Sample Nos. 43 through 73, Y-1 was replaced with one of Y-2 through Y-6; M-1 with one of M-2 through M-9; C-1 and C-2 with C-3 through C-9; an antistain agent AS-1 with one of AS-2 and AS-3; high-boiling organic solvents DNP, DOP and DIDP with DBP, TOP, TCP, TINP, TEHP, DCPP and THP; a stabilizer ST-1 with one of ST-5, ST-6 and ST-7; a stabilizer ST-3 with one of ST-7, 8, 10 and 11; UV absorbers UV-1 and UV-2 with UV-3, UV-4 and UV-5.

[0096] It was found that the above samples had the effects of the invention as well.

DBP :

Dibutyl phthalate

TOP :

Trioctyl phosphate

THP :

Trihexyl phosphate

TCP :

Tricresyl phosphate

TEHP:

Tri(2-ethylhexyl)phosphate

TINP:

Triisononyl phosphate

DCPP:

Dicresyl phenylphosphate

Example 4

[0097] Sample Nos. 74 through 87 were prepared in the manner identical to Sample No. 2 in Example 1 except that the colloidal silver in BC Layers 1 and 2, the dyes in Layers 1, 3 and 6 were changed as shown in Table 4. The amount of colloidal silver was the same as that of Sample No. 2, and the amounts of the dyes were 0.005 g/m in Layer 1, 0.004 g/m in Layer 3, and 0.009 g/m in layer 6.

[0098] Each sample was exposed and processed in the same manner as in Example 2, and was evaluated for fogging and sharpness as well.

[0099] The results are summarized in Table 4.

[0100] As is apparent from the results thereof, good sharpness is attained in every sample containing colloidal silver in the BC layers. It is also apparent that colloidal silver used in combination with the dye of the invention can provide the good photographic properties while the combination of colloidal silver and the comparative dye increases fog in Processing B.

Example 5

[0101] Sample No. 88 to 107 were prepared in the same manner as in Sample No. 2 of Example 1 except that the colloidal silver was replaced with an AI dye and the dyes in Layers 1, 3 and 6 were changed as shown in Table 5. The amount of the AI dye was 0.01 g/m, and the amounts of the dyes added to Layers 1, 3 and 6 were the same as in Example 4.

[0102] Each sample was exposed and processed in the same manner as in Example 1, and was evaluated for fog and sharpness, of which results are summarized in Table 5.

[0103] As is apparent from the results thereof, excellent sharpness was shown in every sample containing the AI dye in the BC layers. It has been also found that the dye used in the invention used in combination with the AI dye can provide the excellent photographic properties while the combination of the comparative dye and the AI dye increases fog in Processing B.

Claims

1. A silver halide light-sensitive photographic material for backlighting photodisplay comprising a polyester film support and provided thereon photographic component layers including a silver halide emulsion layer, wherein at least one of the silver halide layers contains silver halide grains having a silver chloride content of 80 mole % or more accounting for not less than 80 mole % of total grains contained in the layer and at least one of the photographic component layers contains a compound represented by the following Formula I:

wherein R₁ to R₆ each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group and a heterocyclic group, provided that one of R₁ and R₂ and one of R₃ and R₄ each represent the groups other than a hydrogen atom and that at least one of R₁ to R₆ has a water-solubilizing group or a substituent having a water-solubilizing group; L₁ to L₅ each represent a methine group; and m and n each represent 0 or 1.

2. The photographic material of claim 1, wherein the silver halide grains comprise silver chloride of 98.5 to 99.9 mole %, silver bromide of 0.1 to 1.5 mole % and silver iodide of 0 to 0.02 mole %.

3. The photographic material of claim 2, wherein the silver halide grains comprise silver chloride of 99.0 to 99.8 mole %, silver bromide of 0.2 to 1.0 mole % and silver iodide of 0 mole %.

4. The photographic material of claims 1, 2 or 3, wherein at least one of the silver halide emulsion layers is blue-sensitive and contains a compound represented by Formula I in which m and n are 0.

5. The photographic material of claims 1, 2, 3 or 4, wherein at least one of the silver halide emulsion layers is green-sensitive and contains a compound represented by Formula I in which m is 1 and n is 0.

6. The photographic material of claim 1, 2, 3, 4 or 5, wherein at least one of the silver halide emulsion layers is red-sensitive and contains a compound represented by Formula I in which m and n are 1.

7. The photographic material of claims 1 or 2 to 6, wherein the content of the compound of Formula I is 0.01 to 10 mg/dm.

8. The photographic material of claim 7, wherein the content is 0.03 to 5.0 mg/dm.

9. The photographic material of claims 1 or 2 to 8, wherein the support is transparent or translucent.

10. The photographic material of claim 9, wherein the translucent support contains a white pigment.

11. The photographic material of claim 9 or 10, wherein the support has an oxygen permeation rate of 2.0 mℓ/m·hr·atm or less.

12. The photographic material of claim 11, wherein the oxygen permeation rate is 1.0 mℓ/m·hr·atm or less.

13. The photographic material of claims 1 or 2 to 12, wherein the photographic component layers further contain colloidal silver or colloidal manganese.

14. The photographic material of claim 13, wherein the photographic component layers contain colloidal silver.

Ansprüche

1. Lichtempfindliches photographisches Silberhalogenidmaterial für die Belichtung eines Photodisplays mit Schwarzlicht (unsichtbarem Licht), das umfaßt einen Polyesterfilm-Träger, auf den photographische Komponentenschichten aufgebracht sind, die mindestens eine Silberhalogenidemulsionsschicht umfassen, wobei mindestens eine der Silberhalogenidemulsionsschichten Silberhalogenidkörnchen mit einem Silberchloridgehalt von 80 Mol-% oder mehr enthält, die nicht weniger als 80 Mol-% der Gesamtanzahl der in der Schicht enthaltenen Körnchen ausmachen, und mindestens eine der photographischen Komponentenschichten eine Verbindung der folgenden Formel (I) enthält:

worin bedeuten:

R₁ bis R₆   jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkenylgruppe und eine heterocyclische Gruppe, mit der Maßgabe, daß mindestens einer der Reste R₁ und R₂ und einer der Reste R₃ und R₄ jeweils die von einem Wasserstoffatom verschiedenen Gruppen darstellt und mindestens einer der Reste R₁ bis R₆ eine wasserlöslichmachende Gruppe oder einen Substituenten mit einer wasserlöslichmachenden Gruppe aufweist;

L₁ bis L₅   jeweils eine Methingruppe; und

m und n   jeweils die Zahl 0 oder 1.

2. Photographisches Material nach Anspruch 1, worin die Silberhalogenidkörnchen 98,5 bis 99,9 Mol-% Silberchlorid, 0,1 bis 1,5 Mol-% Silberbromid und 0 bis 0,02 Mol-% Silberjodid enthalten.

3. Photographisches Material nach Anspruch 2, worin die Silberhalogenidkörnchen 99,0 bis 99,8 Mol-% Silberchlorid, 0,2 bis 1,0 Mol-% Silberbromid und 0 Mol-% Silberjodid enthalten.

4. Photographisches Material nach den Ansprüchen 1, 2 oder 3, worin mindestens eine der Silberhalogenidemulsionsschichten blauempfindlich ist und eine Verbindung der Formel (I) enthält, in der m und n die Zahl 0 bedeuten.

5. Photographisches Material nach den Ansprüchen 1, 2, 3 oder 4, worin mindestens eine der Silberhalogenidemulsionsschichten grünempfindlich ist und eine Verbindung der Formel (I) enthält, in der m für die Zahl 1 und n für die Zahl 0 stehen.

6. Photographisches Material nach Anspruch 1, 2, 3, 4 oder 5, worin mindestens eine der Silberhalogenidemulsionsschichten rotempfindlich ist und eine Verbindung der Formel (I) enthält, in der m und n die Zahl 1 bedeuten.

7. Photographisches Material nach den Ansprüchen 1 oder 2 bis 6, worin der Gehalt an der Verbindung der Formel (I) 0,01 bis 10 mg/dm beträgt.

8. Photographisches Material nach Anspruch 7, worin der Gehalt 0,03 bis 5,0 mg/dm beträgt.

9. Photographisches Material nach den Ansprüchen 1 oder 2 bis 8, worin der Träger transparent oder durchscheinend ist.

10. Photographisches Material nach Anspruch 9, worin der durchscheinende Träger ein weißes Pigment enthält.

11. Photographisches Material nach Anspruch 9 oder 10, worin der Träger eine Sauerstoffpermeationsrate von 2,0 ml/m.h.at oder weniger aufweist.

12. Photographisches Material nach Anspruch 11, worin die Sauerstoffpermeationsrate 1,0 ml/m.h.at oder weniger beträgt.

13. Photographisches Material nach den Ansprüchen 1 oder 2 bis 12, worin die photographischen Komponentenschichten außerdem kolloidales Silber oder kolloidales Mangan enthalten.

14. Photographisches Material nach Anspruch 13, worin die photographischen Komponentenschichten kolloidales Silber enthalten.

Revendications

1. Matériau photographique sensible à la lumière à base d'halogénure d'argent pour photoaffichage éclairé à contre-jour comprenant un support de film polyester et sur lequel sont fournies des couches composantes photographiques incluant une couche d'émulsion d'halogénure d'argent, où au moins une des couches d'halogénure d'argent contient des grains d'halogénure d'argent ayant une teneur en chlorure d'argent de 80% molaire ou plus représentant au moins 80% molaire du total des grains contenus dans la couche et au moins une des couches composantes photographiques contient un composé représenté par la formule I ci-dessous:

dans laquelle R₁ à R₆ représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcényle et un groupe hétérocyclique, à condition que l'un des radicaux R₁ et R₂ et l'un des radicaux R₃ et R₄ représente des groupes autres qu'un atome d'hydrogène et qu'au moins un des radicaux R₁ à R₆ ait un groupe solubilisant dans l'eau ou un substituant ayant un groupe solubilisant dans l'eau; L₁ à L₅ représentent chacun un groupe méthine; et m et n valent chacun 0 ou 1.

2. Matériau photographique de la revendication 1, dans lequel les grains d'halogénure d'argent comprennent du chlorure d'argent à 98,5 à 99,9% molaire, du bromure d'argent à 0,1 à 1,5% molaire et de l'iodure d'argent à 0 à 0,02% molaire.

3. Matériau photographique de la revendication 2, dans lequel les grains d'halogénure d'argent comprennent du chlorure d'argent à 99,0 à 99,8% molaire, du bromure d'argent à 0,2 à 1,0% molaire et de l'iodure d'argent à 0% molaire.

4. Matériau photographique des revendications 1, 2 ou 3, dans lequel au moins une des couches d'émulsion d'halogénure d'argent est sensible au bleu et contient un composé représenté par la formule I dans laquelle m et n valent 0.

5. Matériau photographique des revendications 1, 2, 3 ou 4, dans lequel au moins une des couches d'émulsion d'halogénure d'argent est sensible au vert et contient un composé représenté par la formule I dans laquelle m vaut 1 et n vaut 0.

6. Matériau photographique de la revendication 1, 2, 3, 4 ou 5, dans lequel au moins une des couches d'émulsion d'halogénure d'argent est sensible au rouge et contient un composé représenté par la formule I dans laquelle m et n valent 1.

7. Matériau photographique des revendications 1 ou 2 à 6, dans lequel la teneur en composé de formule I est de 0,01 à 10 mg/dm.

8. Matériau photographique de la revendication 7, dans lequel la teneur est de 0,03 à 5,0 mg/dm.

9. Matériau photographique des revendications 1 ou 2 à 8, dans lequel le support est transparent ou translucide.

10. Matériau photographique de la revendication 9, dans lequel le support translucide contient un pigment blanc.

11. Matériau photographique de la revendication 9 ou 10, dans lequel le support a une vitesse de pénétration par l'oxygène de 2,0 ml/m.h.atm ou moins.

12. Matériau photographique de la revendication 11, dans lequel la vitesse de pénétration par l'oxygène est de 1,0 ml/m.h.atm ou moins.

13. Matériau photographique des revendications 1 ou 2 à 12, dans lequel les couches composantes photographiques contiennent en outre de l'argent colloïdal ou du manganèse colloïdal.

14. Matériau photographique de la revendication 13, dans lequel les couches composantes photographiques contiennent de l'argent colloïdal.