JPH08314047A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain the photosensitive material capable of forming a high-quality image free from surface gloss and restrained from roller marks due to an automatic developing machine in high sensitivity by incorporating silver halide grains sensitized with a selenium compound in a silver halide emulsion layer and a specified titanium compound in one of photographic sensitive material constituent layers. CONSTITUTION: The silver halide emulsion layer contains the Se-sensitized silver halide grains and at least one of the photographic constituent layers contains the titanium complex represented by the formula in which each of R1 and R2 is, independently, an H atom or a 1-10C alkyl or -CH2 (CHOH)n CH2 -R3 group; Y is a 2-6C linear C cross-linking group; X is an 0 or N atom; Z is a (NR9 R10 R11 R12 )<+> group; (I) is 1 or 2; (n) is an integer of 0-4; R3 is an H atom or a hydroxy group; and each of R9 -R12 is an H atom or a 1-4C alkyl group.

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, and more particularly to a silver halide photographic light-sensitive material in which generation of roller marks by an automatic processor and surface gloss are eliminated.

[0002]

2. Description of the Related Art In recent years, as the demand for laser imagers has increased, demands for rapid processing and high image quality of laser imaging films have been increasing.

As a means for accelerating the processability of a light-sensitive material,
Various methods are known, for example, reducing the amount of a binder such as gelatin or changing the composition of silver halide grains to one having good developability.

However, when the amount of the binder is reduced, the pressure resistance of the silver halide grains is deteriorated and, for example, a spot-like fog called a roller mark is likely to occur on the conveying roller of an automatic developing machine.

On the other hand, laser imaging film and X
Because ray film etc. directly observe the silver image,
There is a demand for an image that has a surface gloss and is easy to read. In particular, since it becomes difficult to observe when the surface has a high degree of gloss, silica or polymer beads have been conventionally added to the photosensitive material to make the surface matte and suppress surface reflection.

However, the use of a sufficient amount of the matting agent has a drawback that the haze is lost and there is a problem that the film is devitrified. The use of non-photosensitive silver halide grains having a relatively large grain size in place of such a matting agent is disclosed in, for example, JP-A-6-30527. However, the rapid processability is significantly deteriorated, which is not preferable.

As the roller mark prevention method described above, many proposals have been made, including an anti-pressure agent, but high-quality silver halide photography without losing rapid processability and having no surface gloss. There has been a strong demand for photosensitive materials.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a high-sensitivity and high-quality silver halide photographic light-sensitive material which suppresses the generation of roller marks by an automatic processor and has no image surface gloss. It is in.

[0009]

The objects of the present invention have been solved by the following.

(1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a support, the silver halide emulsion layer is selenium-sensitized halogen. A silver halide photographic light-sensitive material containing silver halide grains and containing a titanium complex represented by the following general formula [1] in at least one layer of the constituent layers of the silver halide photographic light-sensitive material. .

[0011]

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In the formula, R ₁ and R ₂ are each independently a hydrogen atom,
It represents an alkyl group having 1 to 10 carbon atoms or —CH ₂ (CHOH) _n CH ₂ —R ₃ , and Y represents a linear bridging group having 2 to 6 carbon atoms. X is O
Alternatively, in N, Z represents (NR ₉ R ₁₀ R ₁₁ R ₁₂ ) ⁺ and I represents an integer of 1 to 2. n is an integer of 0 to 4, R ₃ is a hydrogen atom or a hydroxy group, and R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

(2) The silver halide photographic light-sensitive material as described in the above item (1), wherein the silver halide grains in the light-sensitive silver halide emulsion layer have an average grain size of 0.3 μm or less.

(3) The silver halide photographic light-sensitive material as described in the above item (1), wherein the content of silver chloride in the silver halide grains of the light-sensitive silver halide emulsion layer is 70 mol% or less.

The present invention will be described in detail below.

The light-sensitive silver halide emulsion according to the present invention is selenium-sensitized and contains a titanium complex represented by the above-mentioned general formula [1] in at least one layer constituting the silver halide photographic light-sensitive material. . In the general formula [1], the alkyl groups represented by R ₁ and R ₂ in the formula may be substituted or unsubstituted. Y of the linear bridging group having 2 to 6 carbon atoms may be unsubstituted or substituted with, for example, a hydroxy group or an alkyl side chain, a carboxyl group or a phenyl group.

In a particularly preferred example, when X and Y are elements necessary for forming a salt of lactic acid, glycolic acid, malic acid, citric acid, tartaric acid, sugar acid, gluconic acid, glyceric acid or mandelic acid. Or R ₁ and R ₂ are glycerol, erythritol, arabitol, xylitol, sorbitol, dulcitol, mannitol,
In this case, it represents an element necessary for forming inositol, glucose, fructose, mannose, galactose, xylose, sucrose, lactose, maltose or cellobiose.

Examples of the compound represented by the general formula [1] of the present invention include the followings, but the present invention is not limited thereto.

[0019]

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[0020]

[Chemical 4]

[0021]

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[0022]

[Chemical 6]

The titanium complex represented by the general formula [1] of the present invention may be added in an amount of 0.0001 to 1.0 g, particularly 0.050 to 100 g per 100 g of gelatin in the silver halide photographic material constituting layer.
It is preferably 0.75 g. In the case of an emulsion, it may be added at any time before the emulsion is coated, but it is preferably after the chemical sensitization or the spectral sensitization. The titanium complex may be added after the selenium sensitization or before, but preferably after.

The addition may be carried out using an aqueous solution or a suitable solvent. When it is added to a hydrophilic colloid layer other than the emulsion layer (for example, a protective layer, an intermediate layer, a dye layer, etc.), it is also added at any time before coating.

In the silver halide emulsion of the present invention, silver bromide, silver iodobromide, silver iodochloride, silver chloroiodobromide, etc. can be used as the silver halide, but the silver chloride content is particularly 70 mol. %, Preferably 10 mol% to 60 mol% of silver chloride, and silver iodobromide or silver bromide is preferable. When silver iodobromide is used, the silver iodide content is 2 mol% or less as the average silver iodide content in the entire silver halide grains.
It is preferably 1 mol% or less, more preferably 0.5 mol% or less.

In the present invention, the emulsion is tabular, cubic,
Any particles such as octahedron, tetrahedron, single crystal and polycrystal may be used. When the silver halide grains contain silver iodide, they are contained on the surface and / or inside, but it is preferable to contain both on the surface / inside.

In the case of the surface, it is particularly preferable to contain it on the outermost surface as described later. In the inside, the tabular silver halide grains have a silver iodide content of 4 at any site.
It has a maximum value of not less than mol%, preferably not less than 4 mol% and not more than 10 mol%.

The silver halide emulsion of the present invention can be chemically sensitized. There are no particular restrictions on the conditions of the chemical ripening, that is, the steps of chemical sensitization, such as pH, pAg, temperature, time, etc., and the conditions generally used in the art can be used. For chemical sensitization, selenium sensitization is used in combination with sulfur-containing compounds capable of reacting with silver ions and sulfur sensitization using active gelatin, reduction sensitization using reducing substances, gold and other noble metals. The noble metal sensitizing method and the like used can be used in combination.

The selenium sensitizers used include a wide variety of selenium compounds. For example, U.S. Pat.No. 1,574,944,
1,602,592, 1,623,499, JP-A-60-150046,
It is described in JP-A-4-25832, 4-109240, 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg,
N, N-dimethylselenourea, N, N, N′-triethylselenourea, N, N, N′-trimethyl-N′-heptafluoroselenourea, N, N, N′-trimethyl-N′-heptafluoro Propylcarbonyl selenourea, N, N, N′-trimethyl-N′-4-nitrophenylcarbonyl selenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenamides (eg, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosate) And a selenide (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. US Patent 1,574,944
Issue 1,602,592, 1,623,499, 3,297,446,
3,297,447, 3,320,069, 3,408,196, 3,4
08,197, 3,442,653, 3,420,670, 3,591,38
5, French Patents 2,693,038, 2,093,209, Japanese Patent Publications 52-34491, 52-34492, 53-295, 57-22090
No. 59-180536, 59-185330, 59-181337.
No. 59, No. 187338, No. 59-192241, No. 60-150046,
60-151637, 61-246738, JP 3-4221, 3-
24537, 3-111838, 3-116132, 3-148648
No. 3, No. 3-237450, No. 4-16838, No. 4-25832, No. 4-32
No. 831, No. 4-96059, No. 4-109240, No. 4-140738, No.
4-140739, 4-147250, 4-149437, 4-184331
No. 4-190225, 4-191729, 4-19535, British Patent 255,846, 861,984. HE Spencer et al. J
It is also disclosed in scientific literatures such as ournal of Photographic Science, 31: 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used.

The addition method may be a method of adding it by dissolving it in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent depending on the properties of the selenium compound to be used, or by previously mixing with a gelatin solution. Or the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

The temperature of the chemical ripening using the selenium sensitizer is
The range of 40 to 90 ° C is preferable. More preferably, the temperature is 45 ° C or higher and 80 ° C or lower. The pH is 4-9, and the pAg is 6-9.
A range of 5 is preferred.

The silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material containing the above-described silver halide emulsion of the present invention, for example, a black-and-white silver halide photographic light-sensitive material (for example, a medical-use photographic material). Materials, printing sensitive materials, negative sensitive materials for general photography, etc.), preferably black and white silver halide photographic light-sensitive materials, and particularly preferably medical light-sensitive materials.

The silver halide photographic light-sensitive material of the present invention may further contain various additives to the silver halide emulsion according to the purpose. Examples of compounds that can be used include Research Disclosure (RD) No. 176
43 (December 1978), No.18716 (November 1979) and N
Examples include those described in o.308119 (December 1989). The places where they are written are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Examples of the support used in the silver halide photographic light-sensitive material of the present invention include those described in the above RD, and suitable supports include polyethylene terephthalate film and the like. An undercoat layer may be provided on the surface of the support to improve the adhesiveness of the coating layer or a corona Discharge, ultraviolet irradiation, etc. may be performed.

The photographic processing of the light-sensitive material of the present invention is carried out, for example, in RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to X.
Treatment with a treatment solution as described in XI, pp. 1011-1012 may be performed.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. For the developer, known agents such as preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants,
A defoaming agent, a toning agent, a water softening agent, a dissolution aid, a viscosity imparting agent and the like may be used as necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0040]

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

Example 1 (Preparation of Silver Halide Emulsion Layer) Preparation of Em-1 (AgBr: AgCl = 70: 30 mol% core / shell type cubic emulsion) 16 g of gelatin was dissolved in 1 liter of water, and 50 After adding 0.4 g of potassium bromide, 6 g of sodium chloride and 0.8 ml of 10% ethanol solution of polyisopropylene-polyoxyethylene-disuccinic acid sodium salt to a container heated to ℃, 1
600 ml of an aqueous solution containing 00 g of silver nitrate and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride were added by the double jet method over about 25 minutes to make a core portion of 20 mol% of silver chloride, and then 100 g of silver nitrate was added. Aqueous solution containing 5
00 ml and 500 g of an aqueous solution containing 40 g of potassium bromide, 14 g of sodium chloride and 0.7 mol of potassium hexachloroiridium (III) in a molar ratio to silver were added by the double jet method over about 30 minutes to give 40 mol% of silver chloride. Was formed to prepare a core / shell type cubic crystal emulsion having an average grain size of 0.28 μm.

Preparation of Em-2 (AgBr: AgCl = 50: 50 mol% Core / Shell Cubic Emulsion) Em-2 was prepared by changing the above aqueous solution and the molar ratio of potassium bromide and sodium chloride in the aqueous solution. It was prepared by

Preparation of Em-3 (AgBr: AgCl = 20: 80 mol% Core / Shell Cubic Emulsion) Em-3 was prepared by changing the above aqueous solution and the molar ratio of potassium bromide and sodium chloride in the aqueous solution. It was prepared by

Preparation of Em-4 (AgBr: AgCl = 50: 50 mol% tabular grain emulsion) In the same manner as Em-3 except that 60 g of NaBr was added to the mixer and the amount of NaCl was reduced to 150 g. Was prepared.

The resulting emulsions of Em-1 to 4 were desalted, 30 g of gelatin was added thereto and the mixture was heated to 55 ° C., and then the spectral sensitizing dyes [A], [B] and [C] shown below were halogenated. Silver 1
It was added at 70 mg, 90 mg and 80 mg per mol, respectively. Then, an appropriate amount of ammonium thiocyanate, chloroauric acid and sodium thiosulfate was added, and as shown in Table 1, triphenylphosphine selenide was added at 1.0 mg per mol of silver halide for selenium sensitization. -
Stabilized with an appropriate amount of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene.

(Preparation of support) Subbing layer Glycidyl methacrylate 50 wt%, methyl acrylate
The thickness of an aqueous dispersion obtained by diluting a copolymer latex consisting of three monomers of 10 wt% and 40 wt% of butyl methacrylate with pure water so that the concentration becomes 10 wt% as an undercoating liquid. A 175 μm polyethylene terephthalate base was prepared.

On one side of the obtained support, gelatin was used as a backing layer, the following antihalation dye 0.1 g / m ² , N, N-
A backing layer liquid consisting of an appropriate amount of ethylenebis- (vinylsulfonylacetamide) and 0.5 g / m ² of the following copolymer was applied.

Next, gelatin and a matting agent (polymethylmethacrylate: average particle size 5) were used as a protective layer for the backing layer.
μm) and KNO ₃ at 30 mg / m ² , C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H at 0.1
A backing layer solution containing g / m ² and an appropriate amount of glyoxal was prepared.

The backing layer and the protective layer were coated simultaneously so that the coating amounts were 3.1 g / m ² and the support was obtained.

[0050]

[Chemical 7]

(Preparation of Sample) The emulsion layer was coated on one side of the obtained support on which the backing layer was not coated. The additives in the emulsion layer are as follows, and the amount of addition is shown per mol of silver halide. Titanium compound of the present invention Amounts in Tables 1 and 2 1-phenyl-5-mercaptotetrazole 10 mg 1,1-dimethylol-1-bromo-1-nitromethane 70 mg trimethylolpropane 14 mg t-butyl-catechol 68 mg polyvinylpyrrolidone (molecular weight 10,000) 950mg Styrene-maleic anhydride copolymer 2.0g Nitrophenyl-triphenylphosphonium chloride 50mg 2-anilino-4,6-dimercaptotriazine 60mg 1,3-dihydroxybenzene-4-ammonium sulfonate 1.7g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 700mg

[0052]

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The following liquid was prepared as a protective layer liquid for this emulsion layer. The added amount is shown as an amount per 1 g of gelatin.

Polymethylmethacrylate (matting agent having an area average particle size of 5 μm) 21 mg Polymethylmethacrylate (matting agent having an area average particle size of 3 μm) 28 mg Glyoxal 40% aqueous solution 15 mg Titanium compound of the present invention Tables 1 and 2

[0055]

[Chemical 9]

[0056]

[Chemical 10]

The coating amount of the emulsion layer was 2.2 g / m ² , the gelatin amount was 1.8 g / m ² , and the gelatin amount of the protective layer was 1.0 g / m ^2. Prepared.

(Evaluation) Sensitivity, Fog,
Gloss and roller marks were evaluated.

Sensitivity and Fog: When grayscale exposure is performed with a semiconductor laser of 670 nm, the logarithm of the reciprocal of the exposure amount giving Fog + 1.0 is calculated as the sensitivity, and the relative sensitivity when the sensitivity of Sample No. 1 is 100. Indicated. Fog represents the density when an unexposed sample was processed.

Gloss: The sample was exposed with a 670 nm semiconductor laser until the maximum density was reached, and after the following treatment,
The gloss level on the emulsion side was measured with a digital revolution gloss meter VG-ID type (manufactured by Nippon Denshoku Industries Co., Ltd.) at a light incident angle of 20 °. The obtained measured values were evaluated as follows.

Less than 20: Very low gloss 20-25: Low gloss 25-30: Practically no problem 30-35: High gloss 35 or higher: Very high gloss.

Roller mark: A sample exposed to a density of 1.0 was visually evaluated on a film developed by the following method.

Evaluation Criteria ⊚: No pressure spots ○: Light spots scattered around the edges of the film when observed, but practically no problem △: Light spots scattered in the center of the film, but no problems in practice X: Light spots scattered around the film edge, which is a problem in practical use. XX: Dark spots scattered around the center and the edge of the film.
Impractical.

For the development processing, SRX-503 (manufactured by Konica Corporation) was modified, and all the processing steps of Dry to Dry were carried out in the 30-second mode in the following steps.

The treating agent and the treating process are as follows.

(Developer composition) Part A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriamine-5-acetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 140 mg 1-phenyl-5 -Mercaptotetrazole 250mg 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 102g Hydroquinone 390g Diethylene glycol 550g Add water to make 6000ml.

Part B (for 12 l finishing) Glacial acetic acid 70 g 5-Nitroindazole 0.6 g Glutaraldehyde (50% solution) 8.0 g n-Acetyl-D, L-penicillamine 1.2 g Starter glacial acetic acid 120 g HO (CH ₂ ) ₂ S _{(CH 2) 2 S (CH} 2) 2 OH 1g KBr 225g CH 3 N (C 3 H 6 NHCONHCH 2 SC 2 H 5) was added to ₂ 1 g water finish 1l.

(Fixer composition) Part A (for finishing 18.3 l) Ammoniu thiosulfate (70 wt / vol%) 4500 g anhydrous sodium sulfite 450 g sodium acetate trihydrate 450 g boric acid 110 g tartaric acid 60 g sodium citrate 10 g gluconic acid 70 g 1 -(N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18g Glacial acetic acid 330g Aluminum sulfate 62g Finish with pure water to 7200ml.

For the preparation of the developing solution, parts A and B were simultaneously added to about 5 liters of water, water was added while stirring and dissolving to make 12 liters, and the pH was adjusted to 10.53. This is used as a development replenisher.

20 ml of the above-mentioned starter was added to 1 liter of this replenisher, and the pH was adjusted to 10.30 to prepare a working solution. For the fixer, add Part A to approximately 5 liters of water, add water while stirring and dissolve to make 18.3 liters, and adjust the pH with sulfuric acid and ammonia.
Adjust to 4.6 and use this as the fixer replenisher. Treatment process Process temperature (℃) Treatment time (sec) Development + Crossover 35 11.2 Fixing + Crossover 33 7.8 Washing + Crossover 18 6.3 (Supplying water 7 liters / min) Squeeze 40 4.3 Drying 45
6.4 Total --- 36.0 The obtained results are shown in Tables 1 and 2 below.

[0071]

[Table 1]

[0072]

[Table 2]

As is apparent from the table, the sample of the present invention has high sensitivity, no roller mark is generated, and the gloss is very small.

[0074]

As demonstrated in the examples, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material in which generation of roller marks by an automatic processor is suppressed and the surface glossiness of an image is small.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a support, wherein the silver halide emulsion layer is selenium-sensitized halogenated. A silver halide photographic light-sensitive material containing silver particles and containing a titanium complex represented by the following general formula [1] in at least one layer of the silver halide photographic light-sensitive material constituting layers. Embedded image In the formula, R ₁ and R ₂ are each independently a hydrogen atom and a carbon number of 1 to
10 represents an alkyl group or —CH ₂ (CHOH) _n CH ₂ —R ₃ , and Y represents a linear bridging group having 2 to 6 carbon atoms. X is O or N,
Z represents (NR ₉ R ₁₀ R ₁₁ R ₁₂ ) ⁺ and I represents an integer of 1 to 2. n is an integer of 0 to 4, R ₃ is a hydrogen atom or a hydroxy group, and R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains in the light-sensitive silver halide emulsion layer have an average grain size of 0.3 μm or less. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide content of the silver halide grains in the light-sensitive silver halide emulsion layer is 70 mol% or less.