JPH0534865A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the direct positive silver halide photographic sensitive material good in spectral, characteristics, absorbing safelight, free from fog, extremely reduced in color stains due to residual dyes by almost removing dyes by development processing and incorporating a dye having inactive characteristics to photophotographic emulsion. CONSTITUTION:The direct positive silver halide photographic sensitive material having on a support at least one of silver emulsion layer contains a compound represented by formula I in which each of R1-R4 is H, carboxy, alkyl, cycloalkyl, alkenyl, aryl, or a heterocyclic group; and each of X1 and X2 is oxygen or S atom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive silver halide photographic light-sensitive material, and more particularly to a direct positive silver halide photographic light-sensitive material having less residual color contamination.

[0002]

2. Description of the Related Art Generally, in a silver halide photographic light-sensitive material, a dye having a function of absorbing light of a specific wavelength is added to the light-sensitive material in order to prevent a filter, halation, irradiation, or adjust the sensitivity of a photographic emulsion. It is known to contain.

Dyes used for such purposes have good spectral characteristics according to the purpose of use,
Completely decolorized during development, no residual color contamination by dye after development, no adverse effects such as fog and desensitization on photographic emulsion, excellent stability over time in light-sensitive materials, etc. Must satisfy the conditions of.

Many studies have been attempted so far to satisfy the above-mentioned conditions, for example, British Patent 506,385 and US Patent.
3,247,127, Japanese Examined Sho 39-22069, Japanese Examined Sho 43-13168,
US Patent 1,845,404, US Patent 2,493,747, US Patent
2,843,486, West German Patent 616,007, JP-A-48-85130,
49-99620, 49-114420, 49-129537, 50-2
Techniques relating to dyes have been proposed in 8827, 52-108115, 57-185038, 59-24845, and the like.

[0005]

However, the fact is that no dye satisfying all of the above conditions has been obtained by any of the above-mentioned prior arts.

Therefore, the present invention has good spectral characteristics, particularly in a direct positive silver halide photographic light-sensitive material, it absorbs safelight light and does not cause fog.
It is an object of the present invention to provide a direct positive silver halide photographic light-sensitive material containing a dye that is decolorized during development processing and has very little residual color stain after processing and has a property of being inert to a photographic emulsion.

[0007]

The present inventor has achieved the present invention as a result of extensive studies to achieve the above object.

That is, the direct positive silver halide photographic light-sensitive material according to the present invention is a direct positive silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support and is represented by the following general formula [I ] It is characterized by containing the compound represented by these.

[0009]

[Chemical 2] [Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom,
It represents a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and X ₁ and X ₂ each represent an oxygen atom or a sulfur atom. ]

The present invention will be described in more detail below.

As the alkyl group represented by R _{1 to} R ₄ ,
Examples thereof include a methyl group, an ethyl group, a propyl group, an i-propyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a pentadecyl group and an eicosyl group. The alkyl group includes those having a substituent, and examples of the substituent include a halogen atom (eg, each atom of chlorine, bromine, iodine, fluorine, etc.), an aryl group (eg, phenyl group, naphthyl group, etc.), a heterocycle. Group (eg pyrrolidyl group, pyridyl group etc.), sulfinic acid group, carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (eg amino group, diethylamino group etc.), alkoxy group (eg methoxy group, ethoxy group, butoxy group) Group, octyloxy group,
i-propoxy group etc.), aryloxy group (phenoxy group, naphthyloxy group etc.), carbamoyl group (eg aminocarbonyl group, methylcarbamoyl group, pentylcarbamoyl group, morpholinocarbonyl group, phenylcarbamoyl group etc.), amide group (eg Methylamide group, benzamide group, octylamide group, etc.), sulfamoyl group (eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, morpholinosulfonyl group, butylsulfamoyl group, etc.), sulfonamide group (eg, methanesulfone) Amide group, heptanesulfonamide group, benzenesulfonamide group, etc.), sulfinyl group (eg, methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, octylsulfinyl group, and other alkylsulfinyl groups) Group, arylsulfinyl group such as phenylsulfinyl group), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, 2-hydroxyethoxycarbonyl group, octyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group) , Naphthyloxycarbonyl groups, etc.), alkylthio groups (eg methylthio groups,
Ethylthio group, hexylthio group etc.), arylthio group (eg phenylthio group, naphthylthio group etc.), alkylcarbonyl group (eg acetyl group, ethylcarbonyl group, butylcarbonyl group, octylcarbonyl group etc.),
Arylcarbonyl group (eg, benzoyl group, p-methanesulfonamidobenzoyl group, p-carboxybenzoyl group, naphthoyl group, etc.), cyano group, ureido group (eg, methylureido group, phenylureido group, etc.), thioureido group (eg, methylthioureido group) Group, phenylthioureido group, etc.) and the like.

The aryl group represented by R _{1 to} R ₄ includes
Examples thereof include a phenyl group and a naphthyl group. The aryl group includes those having a substituent, and as the substituent,
For example, an alkyl group represented by R _{1 to} R ₄ and R ₁
To the groups described above as the substituents of the alkyl group represented by R ₄ .

Examples of the alkenyl group as a substituent represented by R _{1 to} R ₄ include a vinyl group, an allyl group, a 1-propenyl group, a 1,3-butadienyl group and a 2-pentenyl group. Groups include those having a substituent,
Examples of the substituent include those mentioned above as the substituents of the alkyl group represented by R _{1 to} R ₄ .

The heterocyclic group represented by R _{1 to} R ₄ is
For example, a pyridyl group (2-pyridyl group, 3-pyridyl group,
4-pyridyl group, 5-carboxy-2-pyridyl group,
3,5-dichloro-2-pyridyl group, 4,6-dimethyl-2-pyridyl group, 6-hydroxy-2-pyridyl group,
2,3,5,6-tetrafluoro-4-pyridyl group, 3
-Nitro-2-pyridyl group), oxazolyl group (5-
Carboxy-2-benzoxazolyl group, 2-benzoxazolyl group, 2-oxazolyl group, etc.), thiazolyl group (5-sulfamoyl-2-benzothiazolyl group, 2-
Benzothiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (1-methyl-2-imidazolyl group, 1-methyl-5-carboxy-2-benzimidazolyl group, etc.), furyl group (3-furyl group, etc.), pyrrolyl group ( 3-pyrrolyl group, etc.), thienyl group (2-thienyl group, etc.), pyrazinyl group (2-pyrazinyl group, etc.), pyrimidinyl group (2-pyrimidinyl group, 4-chloro-2-pyrimidinyl group, etc.), pyridazinyl group (2 -Pyridazinyl group, etc.), purinyl group (8-purinyl group, etc.), isoxazolyl group (3-isoxazolyl group, etc.), selenazolyl group (5-carboxy-2-selenazolyl group, etc.), sulforanyl group (3-sulfolanyl group, etc.), Piperidyl group (1-methyl-3-piperidyl group etc.), pyrazolyl group (3-pyrazolyl group etc.),
Tetrazolyl group (1-methyl-5-tetrazolyl group etc.)
Etc., and the heterocyclic groups include those having a substituent group, a substituted alkyl group represented by an alkyl group and R ₁ to R ₄ represented by R ₁ to R ₄ of the as the substituent What was illustrated as a group is mentioned.

Examples of the cycloalkyl group represented by R _{1 to} R ₄ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The cycloalkyl group include those having a substituent, examples of the substituent include those exemplified as the substituents for the alkyl group represented by an alkyl group and R _1, represented by the aforementioned R _1.

When R _{1 to} R ₄ are alkyl groups, the number of carbon atoms is particularly preferably C ₆ or less.

Specific compound examples of the present invention are shown below.
The present invention is not limited to these.

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical formula 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

The compound represented by the general formula [I] of the present invention is used in a direct positive silver halide photographic light-sensitive material so as to have an optical density of 0.05 to 3.0 depending on the purpose.

The photographic constituent layers of the direct positive silver halide photographic light-sensitive material of the present invention include, for example, blue-sensitive emulsion layers, green-sensitive emulsion layers and red-sensitive emulsion layers, intermediate layers, protective layers, filter layers, antihalation layers, There is a photosensitive layer such as an anti-irradiation layer or a non-photosensitive layer.

The compound represented by the general formula [I] of the present invention is preferably contained in the non-photosensitive layer.

The silver halide emulsion used in the light-sensitive material of the present invention may be any of ordinary silver halide emulsions.

As the silver halide used in the emulsion of the light-sensitive material of the present invention, silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide or a mixture thereof is used, but in any case. 60 mol% or more of silver chloride, preferably 80 mol%
It is better to include the above.

The emulsion can be chemically sensitized by a conventional method, or can be optically sensitized to a desired wavelength region by using a sensitizing dye.

The direct positive silver halide emulsion of the present invention comprises
It is preferable to contain rhodium or iridium in the silver halide grains. Rhodium and iridium are used in the form of water-soluble rhodium salt and water-soluble iridium salt.

Examples of the water-soluble rhodium salt used in the present invention include rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, but a complex compound of rhodium trichloride and halogen is preferable,
The water-soluble iridium salt used in the present invention includes iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III) and hexachloroiridium (I
V) Sodium acid and the like. These may be used alone or in combination of two or more.

The addition amount of these is 1 × 10 ^{−6 to} 5 × 10 ⁻² mol per mol of silver halide, but 1 × 10 ⁻⁵ to 1 × 10 ^−4.
Molar is more preferred.

In the present invention, a water-soluble rhodium compound,
The iridium compound is present at the time of preparation of the silver halide emulsion, and the time of preparation means the process of emulsion and physical ripening, and it may be added at any time in this process by any method. However, the preferable addition time is at the time of emulsification, and the particularly preferable method is a method in which a water-soluble rhodium salt or a water-soluble iridium salt is added to the halide solution. The reason is that to maximize the desensitizing effect of rhodium or iridium, rhodium atoms or iridium atoms must be evenly distributed inside and on the surface of silver halide grains. There is a need. On the other hand, those added at the time of physical ripening seem to have rhodium atoms or iridium atoms distributed only on the particle surface, and it is difficult to achieve the purpose of low sensitivity.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened, and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly water-soluble synthetic polymer.

A coupler can be used in the emulsion layer of the direct positive silver halide photographic light-sensitive material of the present invention. Further, a colored coupler having a color correction effect, a competitive coupler and a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, by coupling with an oxidized product of a developing agent, Antifoggant, antifoggant, chemical sensitizer,
Spectral sensitizers, and compounds that release photographically useful fragments such as sensitizers can be used.

Further, the direct positive silver halide photographic light-sensitive material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer. In these layers and / or in the emulsion layer. May contain a dye which is bleached or bleached from the light-sensitive material during the development process.

The direct positive silver halide photographic light-sensitive material of the present invention includes a formalin scavenger, an optical brightener,
Matting agents, lubricants, image stabilizers, surfactants, anti-foggants, development accelerators, development retarders and bleaching accelerators can be added.

As the support for the direct positive silver halide photographic light-sensitive material of the present invention, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

To obtain an image using the light-sensitive material of the present invention, generally known photographic processing can be carried out after exposure.

The direct positive silver halide photographic light-sensitive material of the present invention is exposed with a light source containing a large amount of ultraviolet rays as compared with the conventionally used visible light source. Typical light sources include metal halides, ultra-high pressure mercury, electrodeless lamps (MD, AEL,
V bulb), a quartz halogen light source, and the like. Among them, the quartz halogen light source is preferable because the starting time is short, the lamp price is low, and the maintenance is easy.

[0049]

Example 1 An emulsion was prepared as shown below. Solution [I] Water 7.35 liters Gelatin 93.0 g NaCl 1.83 g Solution [II] 1% Na ₃ RhCl ₆ 15.0 cc Gelatin 50.0 g NaCl 310 g KBr 70 g H ₂ O 1650 cc Finish solution [III] AgNO ₃ 1.0 kg H ₂ O 1650cc finish solution [IV] 1 / 10N HNO ₃ 71cc solution [V] sodium carbonate 8.8 g H ₂ O 660cc finish water 1660cc

Add the solution [IV] into the solution [I] and p
H = 2.0. Then, the solutions [II] and [III] are simultaneously injected into the solution [I] at 35 ° C., EAg = 280 ^mv , pH = 2.0 over 70 minutes, and after aging for 4 minutes, the solution [V] is added. After adjusting the pH to 5.80, desalting was performed by a conventional method. The average grain size of the emulsion was 0.18 μm.

To this emulsion, 0.2 mg of thiourea dioxide and 1.0 mg of chloroauric acid per mol of silver were added, and the mixture was heated to 65 ° C.
It was aged for 60 minutes and gave rise to a frizz.

Further, 500 mg of 5-nitroindazole and 500 mg of the following compound a per mol of silver are added.

[0053]

[Chemical 16] As a bactericide, 10 mg of (A), 3 g of saponin, 3 g of a polymer of styrene maleic acid, and 20 g of a polymer latex of butyl acrylate were added. As a protective film, 1-decyl-2 was added to an aqueous solution of 500 g of gelatin.
-(3-Isopentyl) succinate-2-sodium sulfonate (4 g) was added, and 2 g of amorphous silica having an average particle size of 5 μm was added and dispersed, and the dye of the present invention and the comparative dye were added as shown in Table 1. , The amount of silver is 2.8 g / m ² , and the amount of gelatin in the emulsion layer is 1.5 g on an antistatic processed polyethylene phthalate film described in Japanese Patent Application No. 2-143430.
/ M ² , and the gelatin for the protective layer was applied as 0.8 g / m ² .

The backing layer on the opposite side of the coated surface was 1.6 g of (C-1) in 36 g aqueous solution of gelatin, and (C-
2) 1.9g, saponin 0.2g, (C-3) 5g, styrene-maleic acid polymer 2g, viscosity adjusted, pH adjusted to 5.4 with citric acid, reaction formation of polyglycerol and epichlorohydrin 100 mg of the product was added, and finally, a coating solution containing 140 mg of glyoxal was applied, and the coating amount of gelatin was 2.0 g / m ² and the coating was dried.

At the same time, as a backing protective layer, 2-sulfonate-bis (succinate) (2
-Ethylhexyl) ester sodium salt 340mg, sodium chloride 3g, mucochloric acid 500mg, 500mg of spherical polymethylmethacrylate having an average of 4 μm as a matting agent,
Further, 1 g of glyoxal was added and the coating solution was coated and dried at the same time as the backing layer so that the amount of gelatin was 1.0 g / m ² .

[0056]

[Chemical 17]

[0057]

[Chemical 18] The sample obtained as described above was exposed to FF Shinmei room printer type FA-Q manufactured by Ushio Utech KK through a wedge, and then developed by Konica Corporation, developing solution CDM-621, fixing solution CFL-851, automatic developing machine. 38 ℃ 2 using GR-26
It was treated with 0 ″. The safelight property and the residual color were evaluated by the following methods. The sensitivity was shown as a relative sensitivity when the sensitivity of Sample 3 was 100.

The residual color level was evaluated in 10 steps. 5 or more: Usable level (10: best) 1-4: Unusable results are shown in Table 1.

(2) Safe light test (evaluation of safe light) 50% halftone dot original
The time required for the halftone dot area to decrease by 2% was measured under the light amount of 200 Lux of a fluorescent lamp UV-cut from the sample which was contact-exposed so as to be converted into 55% halftone dot. The results are shown in Table 1.

(3) Aging test In order to examine the influence of aging on photographic performance, thermoprocessing was performed. In the thermo treatment, an unexposed sample was conditioned at 23 ° C. and 55% RH for 3 hours, and then stored in a moisture-proof bag at 55 ° C. for 3 days to be used as a sample for historical use.

[0061]

[Table 1]

[0062]

The present invention has the following effects. Particularly in a direct positive silver halide photographic light-sensitive material having good spectral characteristics, it absorbs safelight light and there is little decrease in Dot%. Decolorized during the development process and very little residual color contamination after the process. It is possible to provide a direct positive silver halide photographic light-sensitive material containing a dye having a property of being inert to a photographic emulsion.

Claims (1)

1. A direct positive silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, containing a compound represented by the following general formula [I]. A direct positive silver halide photographic light-sensitive material characterized in that [Chemical 1] [In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and X ₁ and X ₂ respectively represent Represents an oxygen atom or a sulfur atom. ]