JP2955896B2 - Silver halide photographic material with improved character quality - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for printing which is excellent in the quality of blank characters.

[0002]

2. Description of the Related Art In recent years, photosensitive materials that can be handled in a bright room have become mainstream in the field of printing and plate making. However, such a bright room light-sensitive material has a drawback that the line drawing quality (text quality) when the halftone dot image and the line image are overlaid and exposed is inferior to that of a conventional light-sensitive material handled in a dark room. . Recent demands for a bright room light-sensitive material include not only the quality of the blank characters but also an increase in the illuminance of a fluorescent lamp in order to improve workability. In response to this request, a method of adding a filter dye to the photosensitive material to improve safelight properties in a bright room, and a method of adding a tetrazolium compound or a hydrazine compound to the photosensitive material to improve the quality of blank characters. A method of adding is known. As the filter dye, a water-soluble dye has conventionally been used so that the residual color due to the dye is small. However, such dyes are difficult to fix in a single layer and diffuse widely in the photosensitive material. Therefore, the balance between the change in the blackening rate (dot%) of the halftone dot image with respect to the amount of exposure light and the collapse of the line image. And the line width reproducibility of a blank character at an appropriate exposure amount determined as a light amount at which a halftone dot is reproduced 1: 1 is degraded.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material having a high quality of a blank character. An object of the present invention is to provide a silver halide photographic light-sensitive material having a safelight property and a good decoloring property with little residual color due to a dye.

[0004]

The first object is achieved by a silver halide photographic material having a layer containing a solid fine particle dispersion of a dye represented by the general formula (I). not limited to the dye represented by formula (I), the general
Selected from dyes or compounds VI having at least one carboxyl group represented by the formula (III) or (IV)
That at least one of the at least one well tetrazolium compound and a hydrazine compound of the solid fine particle dispersion of a dye
It has been found that this can be achieved by a silver halide photographic light-sensitive material containing a seed.

[0005]

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In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group,
An aryl group or a ureido group, R ₃ represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group or an aryl group, n represents 1 to 3, and when n is 2 or more, each R ₃ may be the same or different at least one of R ₃ is a nitro group,
At least one of R ₁ , R ₂ and n R ₃ is a group containing a carboxyl group.

Hereinafter, the present invention will be described in more detail.

Each of the groups represented by R ₁ , R ₂ and R ₃ in the formula (I) includes those having a substituent. Examples of the substituent include a carboxyl group, a sulfonamide group, an alkoxy group and a cyano group. , An alkyl group and a hydroxyl group.

Next, specific examples of the dye represented by formula (I) will be shown.

[0010]

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[0011] As a dye having at least one carboxyl group, in addition to the dye represented by formula (I), formula (III), mentioned as the preferred dyes those represented by (IV) and compounds VI.

[0012]

[0013]

[0014]

[0015]

[0016]

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In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ represent an alkyl group, —COOR ₇ (R ₇ represents a hydrogen atom or an alkyl group), a cyano group or an alkoxy group. R ₁ , R ₂ , R
_At least one of ₃ , R ₄ , R ₅ and R ₆ is a group having a carboxyl group or a carboxyl group. R ₁ , R ₂ , R ₃ ,
The alkyl group, alkoxy group represented by R ₄ , R ₅ , and R ₆ and the alkyl group represented by R ₇ include those having a substituent. Examples of the substituent include a carboxyl group, a cyano group, and an alkoxy group. Is mentioned.

Specific examples of the dye represented by formula (III) are shown below.

[0019]

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[0020]

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In the formula, R ₁ is a hydrogen atom, a halogen atom, -C
OOM ₁ , —SO ₃ M ₂ , a nitro group, an alkyl group or an aryl group, R ₂ is a halogen atom or a nitro group, M ₁ and M ₂ are a hydrogen atom, a sodium atom or a potassium atom, X is NH,
M represents 1 or 2, and n represents 1 to 3, and when m and n are 2 or more, each R ₁ and R ₂ may be the same or different, and at least one of m R ₁ One is a group having a carboxyl group or a salt thereof, or a carboxyl group or a salt thereof.

Specific examples of the dye represented by formula (IV) are shown below.

[0023]

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[0024]

[0025]

[0026]

[0027]

[0028]

Specific examples of the dyes having at least one carboxyl group in addition to the dyes represented by the general formulas (I) , (III) and (IV) include the following.

[0030]

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The solid fine particle dispersion of the dye is prepared by pulverizing the dye with a disperser such as a ball mill or a sand mill, and hydrophilic colloid such as water or gelatin, sodium dodecylbenzenesulfonate, fluorinated sodium octylbenzenesulfonate, saponin, nonyl. It can be obtained by dispersing with a surfactant such as phenoxy polyethylene glycol.

The average particle diameter of the solid dye fine particles is 10
μm or less, particularly preferably 1.0 μm or less.

The place where the solid fine particle dispersion of the dye is added is preferably added at least to the silver halide emulsion layer or the emulsion-side protective layer which is the outermost layer on the side of the silver halide emulsion. Further, for the purpose of preventing halation or the like, it may be added to the layer between the emulsion layer and the support and / or to the backing surface side, or may be added to the silver halide emulsion layer for the purpose of adjusting irradiation. Is also good. The amount of the dye to be added is preferably 5 mg to 1 g per m ² per dye, and more preferably 10 to 10 g.
~ 800 mg is preferred.

By using a dispersion of a solid fine particle of a dye having at least one carboxyl group and a tetrazolium compound or a hydrazine compound in combination, the quality of the printed character can be improved.
Safelight and bleaching properties can be improved,
When a solid fine particle dispersion of the dye represented by the general formula (I) is used, it has a good blank character quality without being used in combination with a tetrazolium compound or a hydrazine compound.
Further, it is possible to prevent the finished image from deteriorating due to the trace of the transparent tape for plate making used for fixing the original to the pasting base.

Examples of the tetrazolium compound include those represented by the following general formulas (T-1), (T-2) and (T-3).

[0036]

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Where R ₁ , R ₃ , R ₄ , R ₅ , R ₈ , R ₉ , R
₁₀ and R ₁₁ represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and may be a group which forms a metal chelate or a complex, and R ₂ , R ₆ and R ₇ are an allyl group, a phenyl group, a naphthyl Group, heterocyclic group, alkyl group, hydroxyl group, carboxyl group (including salt), alkoxycarbonyl group, amino group, mercapto group, nitro group or hydrogen atom, D represents a divalent aromatic group, represents an alkylene group, an arylene group, an aralkylene group, X ^-
Represents an anion, and n is 1 or 2, and 1 when the compound forms an inner salt. Each of the groups represented by R _{1 to} R ₁₁ includes those having a substituent, and examples thereof include an alkyl group, an amino group, an amide group, a hydroxyl group, an alkoxy group, an acyloxy group, a halogen atom, a carbamoyl group, and an acylthio group. Groups, alkoxycarbonyl groups, carboxyl groups, acyl groups, cyano groups, nitro groups, mercapto groups, sulfoxy groups, and aminosulfoxy groups.
X ^- include the anion represented by, acid halide ions, inorganic or organic acids such as chloride ions, other acid radical of an anionic surfactant, JP 2-29640 (5) page left upper column line 2 From the eye to the lower right column, the 11th line, sulfur atomized ones and the like can be mentioned. Further, specific examples of the cation portion of the tetrazolium compound include compounds (1) to (34) described in the same publication, page (4), upper left column to (5) upper left column.

Specific examples of the tetrazolium compound include, in addition to the following, I-1 to I-27 described in the lower left column on page (6) of JP-A-3-27049.

T-1 2,3,5-triphenyl-2H-tetrazolium chloride T-2 2,3-bis (p-methoxyphenyl) -5-phenyl-2H
-Tetrazolium chloride T-3 2- (p-methoxyphenyl) -3- (p-toluyl) -5-phenyl-2H-tetrazolium chloride The addition amount of the tetrazolium compound is preferably 1 mg to 10 g per mol of silver halide. And especially from 10 mg to
2 g is preferred.

As the hydrazine compound, those represented by the following general formula (H) are preferred.

[0041]

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In the formula, R ₁ represents a monovalent organic residue, R ₂ represents a hydrogen atom or a monovalent organic residue, and Q ₁ and Q ₂ represent a hydrogen atom, an alkylsulfonyl group (having a substituent And X ₁ represents an oxygen atom or a sulfur atom.

Of the compounds represented by the general formula (H), X
Compounds in which ₁ is an oxygen atom and R ₂ is a hydrogen atom are more preferred.

The monovalent organic residue of R ₁ and R ₂ includes an aromatic residue, a heterocyclic residue and an aliphatic residue.

Specific examples of the groups represented by R ₁ and R ₂ are described in JP-A-3-44635, page 11, lower left column, line 20 to (12).
Those described in the second line of the lower left column of the page can be mentioned.

Specific examples of the hydrazine compound include, in addition to the following compounds, (H-1), (H-2), and (H-2) described in the lower left column of page (12) to the lower right column of page (14) of the same publication. -4) to (H-7), (H-
9) to (H-11), (H-13) to (H-46) and JP-A-3-12704.
No. 9 (8) II-1 to II described in the upper right column of the page to the lower left column of the page (10)
-59.

[0047]

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The amount of the hydrazine compound to be added is 10 ^-5 to 10 ^-1 mol, particularly 10 ^-4 to 10 ^-2 per mol of silver halide.
Molar is preferred.

The place where the tetrazolium compound and the hydrazine compound are added includes a silver halide emulsion layer and a non-light-sensitive layer, and a silver halide emulsion layer is particularly preferable.

[0050] In the silver halide photographic material containing a tetrazolium compound, preferably it contains more spiro Biindan compound. As specific examples of the compound spiro Biindan compounds <br/> compounds include the following.

[0051]

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[0052]

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The silver halide photographic light-sensitive material containing a hydrazine compound preferably further contains a mercaptotetrazole compound. The following are specific examples of the mercaptotetrazole compound.

[0054]

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Silver halide grains, silver halide emulsions, chemical sensitization, spectral sensitization, stabilizers, thickeners, hardeners, ultraviolet absorbers, matting agents suitable for the silver halide photographic light-sensitive material of the present invention. , Coating aids, fluorescent brighteners, various additives such as surfactants, binders, supports, undercoat layers, exposure light sources, development processing conditions, processing solutions, etc. are described in JP-A-3-27049 (2). Lines from the lower left column, line 14 to page (14), lower right column, line 11 may be mentioned.

In the silver halide photographic light-sensitive material of the present invention, it is preferable to provide an antistatic layer on at least one side of the support, and the surface specific resistance of the antistatic side is 1.0 × 10 ¹¹ Ω. The following is preferable, especially 8 × 1
0 ¹¹ Ω or less is preferable. The antistatic layer is preferably a layer containing a reactant of a water-soluble conductive polymer, hydrophobic polymer particles and a curing agent, and a layer containing a particulate metal oxide.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, carboxyl groups, and polyethylene oxide groups. Can be Of these groups, sulfonic acid group,
Sulfate groups and quaternary ammonium bases are preferred. The conductive group requires 5% by weight or more per molecule of the water-soluble conductive polymer. In addition, a carboxyl group, a hydroxyl group, an amino group, an epoxy group,
Includes aziridine group, active methylene group, sulfinic acid group, aldehyde group, vinylsulfone group, etc., among which carboxyl group, hydroxyl group, amino group, epoxy group, aziridine group, aldehyde group may be included. preferable. It is necessary that these groups are contained in an amount of 5% by weight or more per minute of the polymer. The number average molecular weight of the water-soluble conductive polymer is from 3000 to 100,000, preferably from 3500 to 50,000.

The metal oxide is preferably tin oxide, indium oxide, antimony oxide, zinc oxide, or a metal oxide obtained by doping these metal oxides with metal phosphorus or metal indium. Is 0.01-1μ
m is preferred.

[0059]

The present invention will be specifically described below with reference to examples.

[0060] Example 1 (dye dispersion) (described in Table) water 1000g gelatin 120g dye into a ball mill container 200g of dodecylbenzenesulfonic acid sodium salt 10g fluorinated octyl benzene carboxylic acid sodium salt 2g matting agent (SiO ₂ average particle size 5μm 5 g and zirconium oxide beads were put therein, sealed, and dispersed in a ball mill for 5 days. The dispersion was obtained except for the beads.

(Preparation of Photosensitive Material) Monodispersed silver chlorobromide (90 mol% of silver chloride) containing 10 ^-5 mol of rhodium per mol of silver was prepared by a controlled double jet method in an acidic atmosphere of pH 3.0. Created. Particle growth was carried out in a system containing 30 mg of benzyladenine per 1000 ml of 1% aqueous gelatin solution. After mixing silver and halide, 600 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added per 1 mol of silver halide, washed with water and desalted.

Thereafter, 60 mg / mol of silver halide was added.
After adding 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene, sulfur sensitization was performed. As a stabilizer after sulfur sensitization
6-Methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added.

The following additives were added to each of the silver halide emulsions so as to have the respective coating amounts, and a 100 μm-thick polyethylene terephthalate having a latex subbing treatment disclosed in Example 1 of JP-A-59-19941 was used. Coated on support.

Latex polymer: styrene-butyl allylate-acrylic acid terpolymer 1.0 g / m ² saponin 200 mg / m ² sodium dodecylbenzenesulfonate 100 mg / m ² hydroquinone 200 mg / m ² styrene-maleic acid copolymer 200 mg / M ² Gallic acid butyl ester 500 mg / m ² 5-Methylbenzotriazole 30 mg / m ² Dye (solid fine particle dispersion) 2-mercaptobenzimidazole-5 sulfonic acid 30 mg / m ² shown in Table 1 1.5 g of inert ossein gelatin / M ² silver amount 2.8 g / m ² The following protective layer was coated on the above emulsion layer.

Emulsion layer protective layer Fluorinated dioctylsulfosuccinate 300 mg / m ² Matting agent: synthetic silica (average particle size 3.5 μm) 100 mg / m ² Acid-treated gelatin 1.2 g / m ² tetrazolium compound or hydrazine compound The following backing layer and protective film layer were coated on the side of the support opposite to the emulsion layer.

Backing layer latex polymer: butyl acrylate-styrene copolymer 0.5 g / m ² saponin 200 mg / m ² backing dye

[0067]

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Ossein gelatin 2.0 g / m ² Backing layer protective film Dioctyl sulfosuccinate 300 mg / m ² Matting agent: methyl methacrylate (average particle size 4.0 μm) 100 mg / m ² ossein gelatin (isoelectric point 4.9) 1.1 / M ² Fluorinated sodium dodecylbenzenesulfonate
Developer shown below exposing the 50 mg / m ² thus obtained samples were developer processed using fixer. The evaluation was performed as follows.

[Formulation of developer] (Composition A) Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-methylbenzotriazole 200 mg 1-phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid ( 90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg The above composition A and composition B were dissolved in 500 ml of water in the order of use when a developer was used, and used after finishing to 1000 ml.

[Formulation of Fixing Solution] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% W / V aqueous solution) 13.6 ml (composition B) pure water (ion-exchanged water) 17 ml sulfuric acid (50% W / V aqueous solution) 4.7 g aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% W / V aqueous solution) 26.5 g fixer Was dissolved in 500 ml of water in the order of composition A and composition B, and used after finishing to 1000 ml. The pH of the fixing solution was about 4.3. [Processing conditions] (Process) (Temperature) (Time) Current image 38 ° C 20 seconds Fixed 28 ° C 20 seconds Rinse at room temperature 20 seconds <Exposure method> US fusion with the spectrum shown in Figure 1 (FUSION 2) An electrodeless discharge tube light source manufactured by the company was mounted under the glass plate, and the original and the photosensitive material were overlaid and exposed on the glass surface so as to be able to evaluate the sticking marks shown in FIG.

<Method for evaluating photographic performance> (1) Trace of pasting In FIG. 2, the net film 2 was placed on the bases 3 and 5 for pasting.
And then fix the periphery of the net film with a transparent scotch tape for plate making. After exposure and development processing, when there is no trace of this tape (pasting trace), "5". A five-point rating was given as "1".

(2) Draft character quality The derailleur character quality is determined by proper exposure such that the halftone dot area of the halftone film 2 in FIG. The image quality at which a line width of 50 μm on the line drawing film 4 in FIG. 2 was reproduced was evaluated, and a five-point evaluation was made with a very good blank character image quality being “5” and the worst level being “1”.

The results are shown in Table 1.

[0074]

[Table 1]

[0075]

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From the results shown in Table 1, it can be seen that the sample of the present invention is excellent in the quality of the blank character and the performance of the sticking mark, and is more excellent when the tetrazolium compound or the hydrazine compound is used.

Example 2 (Preparation of silver halide emulsion) An aqueous solution of sodium chloride and potassium bromide to which an aqueous solution of silver nitrate and a complex of rhodium (6 coordination) were added at 8 × 10 ^-5 mol / mol of silver was added to a gelatin solution. At the same time, they were added and mixed with stirring. After mixing, 6-methyl-4-
Hydroxy-1,3,3a, 7-tetrazaindene was added for stabilization, followed by washing and desalting to obtain a silver chlorobromide emulsion having a particle size of 0.13 μm and containing 1 mol% of silver bromide.

This emulsion was chemically sensitized with sodium thiosulfate trihydrate and a gold chloride complex.

(Preparation of Emulsion Coating Solution) An emulsion coating solution was prepared by adding the following compounds to the above silver halide emulsion.

M-1 600 mg / silver 1 mol T-2 2.5 g / silver 1 mol S-1 200 mg / silver 1 mol Sodium dodecylbenzenesulfonate 25 mg / m ² 5-methylbenzotriazole 550 mg / silver 1 mol

[0081]

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(Preparation of Coating Solution for Protective Layer) Solid disperse dye shown in Table 2 150 mg / m ² matting agent amorphous silica (average particle diameter 10 μm) 20 mg / m ² matting agent amorphous silica (average particle diameter 2 μm) ) 10mg / m ²

[0083]

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(Preparation of Backing Layer Coating Solution) Solid Disperse Dye II-1 150 mg / m ² Solid Disperse Dye V-1 500 mg / m ² Solid Disperse Dye VI-5 500 mg / m ² Natural Saponin 100 mg / m ² Matting agent Poly Methyl methacrylate (average particle size: 8 μm) 25 mg / m ² (Preparation of photographic light-sensitive material) JP-A-59-19941 50 W / m on a subbed polyethylene terephthalate film support having a thickness of 100 μm shown in Example 1 After performing corona discharge at ² min, an antistatic layer was formed on the backing layer side using a roll-fit coating pan and an air knife so as to have the following composition. After drying at 90 ° C for 2 minutes, 140 ° C
For 9 seconds. The thickness of the dried layer was 1 μm, and the surface resistivity was 1 × 10 ⁸ Ω at 23 ° C. and 55% humidity.

[0085]

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Next, on the emulsion side, a silver halide emulsion layer
The protective layer was coated simultaneously by a slide hopper system while adding a hardening agent solution containing formaldehyde and di (vinylsulfonylmethyl) ether, and passed through a cold air set zone.

Next, a backing layer was applied to the backing layer side by a slide hopper method while adding the above-mentioned hardener solution, and set in cold air. Further, both surfaces were simultaneously dried in the drying zone under the following drying conditions. The coating speed is 100m
/ Min, and the transfer after application of the backing layer was performed in a non-contact state until winding after drying.

(Drying conditions) After setting, drying was performed with a drying air at 30 ° C. for 50 seconds until the weight ratio of water / gelatin became 800%.
Then use dry air at 35 ° C and a relative humidity of 30% to reach 200%.
Dry for 5 seconds, apply air for 5 seconds, surface temperature 34 ° C
After 30 seconds from the point when it becomes
-It was dried for 1 minute in air at a relative humidity of 16%.

This photosensitive material was wound up at 23 ° C. and a relative humidity of 55%, cut, and placed in a barrier bag conditioned for 3 hours under the same environment.
After conditioning for 8 hours at 40 ° C. and a relative humidity of 10% for 8 hours, it was sealed together with cardboard which was conditioned for 2 hours at a temperature of 23 ° C. and a relative humidity of 55%.

The coated silver amount of the photosensitive material after drying was 3.5 g / m ² ,
The amount of gelatin in the silver halide emulsion layer was 1.8 g / m ² , the amount of gelatin in the protective layer was 0.8 g / m ² , and the amount of gelatin in the backing layer was 2 g.
/ m ² and the surface smoother value of the photosensitive material after humidity control for 2 hours in an environment of 23 ° C. and 48% relative humidity (Toei Electronics Co., Ltd.)
(Measured by SM-6B manufactured by Co., Ltd.) was 60 mmHg on the emulsion side and 100 mmHg on the backing layer side. As described above, samples II-1 to II- 6 were prepared by changing the kind of the solid disperse dye in the protective layer. Also, instead of T-2 of Samples II-1 to II- 6 , H-
Samples III-1 to III- 6 using 2.5 g / mol of silver were prepared.

Each sample was evaluated as follows.

<Safe light property> The sample was irradiated with a fluorescent lamp for preventing fading (FL40SW-NU manufactured by Toshiba Corporation) under 400 Lux for 30 minutes, developed, and the fog density on the unirradiated portion was measured. When the fog value exceeds 0.004, there is a practical problem. <Quality of blank characters> The same procedure as in Example 1 was performed, except that a five-step evaluation was performed centering on the reproduction width of a line width of 110 μm. Rank 1: Reproducible width is 70 μm or more.

Rank 2: Reproduction width is 70 to 79 μm: the lowest level that can withstand practical use. Rank 3: Reproduction width is 80 to 89 μm: There is no problem in practical use.
Some thin lines collapse. Rank 4: Reproduction width is 90 to 94 μm: Almost all lines are reproduced, but there are some fine lines that are hard to read and difficult to read. Rank 5: Reproduction width is 95 μm or more… All lines are reproduced clearly.

<Decolorization> Each sample was processed without exposure under the following conditions, and five developed samples were superimposed, and the residual color level was visually evaluated on a white paper in five steps. A rank of 2 or less is a level that cannot withstand practical use.

[Development processing conditions] (Process) (Temperature) (Time) Development 28 ° C 30 seconds Fixing 28 ° C 20 seconds Water washing Normal temperature 15 seconds Squeeze drying 40 ° C 35 seconds [Developing machine] Automatic development by Konica Corporation GR-27 [Developer formulation] Hydroquinone 45.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 15.0 g Potassium hydroxide 55.0 g 5-Sulfosalicylic acid 45.0 g Boric acid 35.0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium salt 1.0 g Potassium bromide 6.0 g 5-methylbenzotriazole 0.6 g n-butyldiethanolamine 15.0 g Add water 1000 ml (pH = 11.6) [Fixing solution formulation] (Composition A) Ammonium thiosulfate (72.5% (W / V aqueous solution) 230ml Sodium sulfite 9.5g Sodium acetate trihydrate 15.9g Boric acid 6.7g Sodium citrate dihydrate 2g Acetic acid (90% W / W aqueous solution) 8.1ml (Composition B) Pure water (ion exchange water) ) 17ml sulfuric acid (50% W / W aqueous solution) 5.8 g Aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% W / W aqueous solution) 26.5 g fixer above composition A in water 500ml when using the composition B, was dissolved in this order, 1000 ml And used. PH of this fixer
Was 4.3.

The above results are shown in Tables 2 and 3.

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

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As is evident from Table 2, the sample of the present invention is excellent in safelight property, blank character quality, and decolorization property. Particularly, when a tetrazolium compound and a spiropyran compound are used in combination, a hydrazine compound and a mercaptotetrazole compound are used in combination. In this case, it can be seen that it is even better.

Similar results were obtained when the automatic developing machine was changed to that shown in FIG. 3 and the following processing steps were performed.

(Process) (Temperature) (Time) Development 40 ° C for 15 seconds Fixing 34 ° C for 15 seconds Rinse with water Normal temperature 9 seconds Squeeze drying 40 ° C 9 seconds

[0103]

According to the present invention, the quality of blank characters, the quality of pasting marks, the safelight property and the decoloring property of a silver halide photographic light-sensitive material for printing can be improved.

[Brief description of the drawings]

FIG. 1 is a diagram showing a spectrum of a light source.

FIG. 2 shows a positional relationship between a blank character, a document at the time of returning operation, and a photosensitive material.

FIG. 3 is an explanatory diagram of an automatic developing machine.

[Explanation of symbols]

 1 Photographic material for return 2 Halftone image film 3,5 Pasting base 4 Film of line drawing positive image 6 Cut mask film 11 Insert table 12 Detection-Development transfer rack 13 Developing rack 14 Developing-Fixing transfer rack 15 Fixing rack 16 Fixing- Washing rack 17 Washing rack 18 Squeeze rack 19 Drying guide 20 Guide 21 Drying outlet rack 22 Film basket

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-191942 (JP, A) JP-A-2-226143 (JP, A) JP-A-4-14033 (JP, A) JP-A-4-1993 255843 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 1/06 501 G03C 1/83

Claims (5)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a layer containing a solid fine particle dispersion of a dye represented by formula (I). Embedded image [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group or a ureido group, R ₃ represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group or an aryl group, and n represents 1 to 3, When n is 2 or more, each R ₃ may be the same or different, at least one of R ₃ is a nitro group, and R ₁ , R ₂
And at least one of n R ₃ is a group containing a carboxyl group. ] 2. A compound represented by the following general formula (III) or (IV)
The dye having at least one carboxyl group is
Is a silver halide photographic light-sensitive material containing a dispersion of solid fine particles of a dye selected from compound group VI and at least one tetrazolium compound. [A] [In the general formula (III), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ is an alkyl group, —COOR ₇ (R ₇ is a hydrogen atom or an alkyl
Represents a hydroxyl group . ), Represents a cyano group or an alkoxy group,
At least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ is a cal
It is a group having a boxyl group or a carboxyl group.
Alkyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ ;
The alkoxy group and the alkyl group represented by R ₇ represent a substituent
And the substituent is, for example, carboxy
Examples include a sil group, a cyano group, and an alkoxy group. Embedded image In the general formula (IV), R ₁ is a hydrogen atom, a halogen atom
--COOM ₁ , --SO ₃ M ₂ , nitro group, alkyl group or ant
The Lumpur group, R ₂ represents a halogen atom or a nitro group, M _1, M
₂ represents a hydrogen atom, a sodium atom or a potassium atom;
Is NH, a sulfur atom or an oxygen atom, m is 1 or 2, n is 1
And when m and n are 2 or more, R ₁ and R ₂ are the same.
And at least one of the m R ₁ is
Boxyl group or group having a salt thereof or carboxyl
Or a salt thereof. ] [Of C] 3. The silver halide photographic light-sensitive material according to claim 2, comprising at least one spirobiindane compound. 4. A compound represented by the general formula (III) or (IV)
The dye having at least one carboxyl group is
Is a silver halide photographic light-sensitive material containing at least one dispersion of solid fine particles of a dye selected from compound group VI and a hydrazine compound. 5. The silver halide photographic material according to claim 4, comprising at least one mercaptotetrazole compound.