JPH07219089A - Silver halide photographic sensitive material for x-rays - Google Patents

Abstract

PURPOSE:To provide a silver halide photosensitive material for x-ray photography freed of residual dye stains due to rapid processing and superior in image sharpness, and pure in the black color tone of silver image. CONSTITUTION:The photosensitive material having at least 2 silver halide emulsion layers on one side of a support contains a spectral sensitizing dye in the silver halide emulsion layer formed nearest the support in an amount of 2.0 to 7.0mg/m<2> on one side of the support and in that farthest from the support in an amount of >=7.5mg/m<2> on one side of the support.

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 X-rays, which is free from residual color contamination even after rapid processing, has excellent image sharpness, and has a pure black tone of image silver. Regarding

[0002]

2. Description of the Related Art In order to improve the image quality of silver halide photographic light-sensitive materials, it is important to improve the sharpness of images. Especially direct X
In the case of a silver halide photographic light-sensitive material having an emulsion layer on both sides of a support like a medical film for lines, deterioration of sharpness due to the crossover light effect becomes a problem.

Various methods have been proposed in the past for cutting off the crossover light. For example, a method of increasing the light absorption amount by using a large amount of a spectral sensitizing dye in silver halide grains, or containing a dye. A method of providing a dye layer composed of a mordant under the photosensitive emulsion layer has long been known.

However, all of these methods have the drawback that residual color contamination occurs during rapid processing of the light-sensitive material.

In recent years, photographic materials have been rapidly processed and the replenishment of processing solution has been rapidly reduced, and the desired sensitivity and maximum density can be obtained in a short time, and high sharpness without residual color contamination. Images are required.

It is also known to use tabular silver halide grains for accelerating the developability, but the grains increase the covering power, but on the other hand, the problem that the color tone of the image silver after processing is yellowish. Had. In medical photographic light-sensitive materials, image color tone and contamination are extremely important for image observers, and silver halide photographic light-sensitive materials capable of obtaining clear and pure black tone images are desired.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic which, even if it is rapidly processed, has no residual color contamination, has excellent image sharpness, and can obtain a pure black tone of image silver. To provide a light-sensitive material.

[0008]

The above objects of the present invention are as follows.
In a silver halide photographic light-sensitive material having at least two silver halide emulsion layers on at least one side of the support, the spectral sensitization contained in the silver halide emulsion layer closest to the support. Dye amount is 2.0 mg per side
X is 7.0 mg / m ² or less, and the amount of the spectral sensitizing dye contained in the silver halide emulsion layer farthest from the support is 7.5 mg / m ² or more on one side. This is achieved by a silver halide photographic light-sensitive material for lines.

The present invention will be described in detail below.

The spectral sensitizing dye referred to in the present invention usually means cyanine, merocyanine and the like which are used for photography, and the carbocyanine dyes described in JP-A-5-113619 are particularly preferable. Specific examples thereof include spectral sensitizing dyes represented by the following general formula [I], [II] or [III].

[0011]

[Chemical 1]

In the general formula [I], R ₁ , R ₂ and R ₃ are substituted or unsubstituted alkyl groups having a carbon number of 4 or less or lower alkyl groups or hydroxyalkyl groups such as 2-hydroxyethyl, 4-hydroxybutyl and the like. , 2-acetoxyethyl, 3-acetoxybutyl etc. as acetoxyalkyl group, carboquinmethyl, 2-carboxyethyl, 3-carboxypropyl, 2- (2-carboxyethoxy) ethyl etc. as carboxyalkyl group, 2 as sulfoalkyl group -Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl and the like can be mentioned.

However, as described above, at least one of R ₁ , R ₂ and R ₃ is a sulfoalkyl group or a carboxyalkyl group.

[0014] Further, X ₁ in the formula [I] ^- as the anion represented by, for example, chloride, bromide, iodide ion, thiocyanate ion, sulfate ion, perchlorate ion, p- toluenesulfonate ion, Examples thereof include ethyl sulfate ion.

Next, typical examples of the compound represented by the general formula [I] will be given.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

As the dye represented by the general formula [I] of the present invention, in addition to the above specific examples, for example, Japanese Patent Application No. 2-11127.
I-1, I-4, I-6, I-7, I-9 to I-1 of the compound examples described on pages 9 to 19 of the specification No. 8
3, I-15, I-16, I-I8 to I-21, I-24 to 33, I
-35 to 40 and the like can be used.

[0020]

[Chemical 5]

Next, in the general formula [II], R ₆ represents a hydrogen atom, a lower alkyl group or an aryl group, and examples of the lower alkyl group include groups such as methyl, ethyl, propyl and butyl. Examples of aryl groups include, for example, phenyl groups.

Examples of R ₄ and R ₆ include those exemplified as R ₁ and R ₃ in the general formula [I] in the general formula [I].

As the anion of X ₂ ⁻ , those exemplified as X ₁ ^{− in the} formula [I] can be mentioned.

Next, typical specific examples of the compound represented by the general formula [II] will be given, but of course the present invention is not limited to this example.

[0025]

[Chemical 6]

[0026]

[Chemical 7]

As the dye represented by the general formula [II] of the present invention, in addition to the specific examples described above, for example, Japanese Patent Application No. 2-111278.
II-3, II-4, II-6, II-7, II-8, II-10 of the compound examples described on pages 20 to 28 of the specification.
II-13, II-14, II-16, II-17, II-18, II-20, I
I-21, II-24 to II-44 and the like can be used.

[0028]

[Chemical 8]

Next, in the general formula [III], the lower alkyl group for R ₇ and R ₉ is methyl, ethyl, propyl,
Examples thereof include groups such as butyl. As the substituted alkyl group,
The groups exemplified as R _{1 to} R ₃ in the general formula [I] can be mentioned.

Examples of the lower alkyl group for R ₈ and R ₁₀ are the same as those for R ₇ and R ₉ . Examples of the hydroxylalkyl group, sulfoalkyl group and carboxyalkyl group for R ₈ and R ₁₀ include the groups exemplified for R _{1 to} R ₃ in the general formula [I].

As the anion of X ₃ ⁻ , those exemplified as X ₁ ^{− in the} general formula [I] can be mentioned.

Typical specific examples of the compound represented by the general formula [III] are shown below.

In this case, of course, the present invention is not limited to this example.

[0034]

[Chemical 9]

As the dye represented by the general formula [III] of the present invention, in addition to the specific examples described above, for example, Japanese Patent Application No. 2-1112.
Compound examples III-1, III-5, III-7 and the like described on page 29 to page 31 of No. 78 can be used.

The sensitizing dye represented by the above-mentioned general formula used in the present invention is "Heterocycrlic compounds Cya" by FM Hamer.
ninedyes and related compounds ”(Heterocyclic Compounds-Cyanine and Randomized Compounds) IV.V.VI, Chapter 89-199 John wile
y & sons (new yok.london) 1964, or DMStur
mer “Heterocycrlic compounds special topics in
Heterocycrlic chemistry ”(Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry) Chapter VIII IV.482-515 John W
It can be easily synthesized based on the method described in iley & sons (new yok london), 1977, etc.

It should be noted that all of the above general formulas show only one state of the resonance structure, and represent the same substance even if they are expressed in an extreme state where the + charge enters a symmetrical heterocyclic nitrogen atom. It is a thing.

The present invention is a silver halide photographic light-sensitive material having at least two silver halide emulsion layers on at least one side of a support. That is, at least two photosensitive silver halide emulsion layers are provided on one side of the support, and the amount of the spectral sensitizing dye contained in the silver halide emulsion layer closest to the support is one side. 2.0m
g / m ² or more and 7.0 mg / m ² or less, and the amount of the spectral sensitizing dye contained in the silver halide emulsion layer farthest from the support is 7.5 mg / m ² or more per side. It is a feature.

Such a layer structure is also applied to the opposite surface of the support, and is applicable to so-called double-sided coated silver halide photographic light-sensitive material for X-ray.

In the present invention, the silver halide emulsion used in the emulsion layer closest to the support need not have substantial photosensitivity, and the position farthest from the support adjacent to the layer is It is desirable that the silver halide emulsion layer (1) has high sensitivity.

In the present invention, as a layer other than the silver halide emulsion layer of the present invention, an undercoat layer, an intermediate layer, an antistatic layer, a filter layer, a protective layer or the like which is usually used may be appropriately combined and formed. it can.

The addition amount of the spectral sensitizing dye according to the present invention is determined by the amount capable of improving the sharpness of an image together with the spectral sensitizing property. That is, when the amount of the dye is small and insufficient, there is no residual color contamination, but the spectral sensitization is low and the high sharpness aimed at by the present invention cannot be obtained. On the contrary, when the amount of the dye is excessive, the residual color contamination is increased, and the spectral sensitization causes desensitization, which is not preferable.

The amount of the spectral sensitizing dye contained in the silver halide emulsion layer closest to the support was 2.0 mg per side.
/ M ² or more and 7.0 mg / m ² or less, more preferably 2.4 mg /
It is not less than m ^{2 and not} more than 5.5 mg / m ² . The amount of the spectral sensitizing dye contained in the silver halide emulsion layer farthest from the support is 7.5 mg / m ² or more per side, and more preferably
It is 8.5 mg / m ² or more and 12.0 mg / m ² or less.

The spectral sensitizing dye according to the present invention is added at a time from the nucleation step of the silver halide emulsion according to the present invention to the end of the desalting step, whereby the spectral sensitization efficiency is excellent. High-sensitivity silver halide emulsion can be obtained,
Further, a spectral sensitizing dye which is the same as or different from the dye added to the above process (from the nucleation process to the end of the desalting process) at any time after the completion of the desalting process, through the chemical ripening process and immediately before the coating process. May be added additionally. The preferred addition time is during the chemical ripening step, particularly preferably at the start of chemical ripening.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse referred to here, when measuring the average particle diameter by a conventional method,
At least 95% by number or weight of grains are silver halide grains having an average grain size within ± 40%, preferably within ± 30%.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may be composed of different silver halide compositions inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a high silver iodide core portion is covered with a low silver iodide shell layer may be used.

The method for producing the above-mentioned monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like. The emulsion used in the silver halide photographic light-sensitive material of the present invention can be grown by, for example, using a seed crystal as a method for obtaining the above monodisperse emulsion, and using this seed crystal as a growth nucleus to supply silver ions and halide ions. Other emulsions may be used.

A method for producing the above core / shell type emulsion is well known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain size / grain thickness) of 3 or more. As an advantage of such tabular grains, it is disclosed in, for example, British Patent No. 2,112,157, U.S. Patents 4,414,310, 4,434,226 etc. as improvement in spectral sensitization efficiency and improvement in image graininess and sharpness can be obtained. The emulsion can be prepared by the methods described in these publications.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image on the grain surface, an internal latent image type which forms a latent image inside the grain, or a type which forms a latent image on both the surface and the inside. It may be an emulsion.

These emulsions are used at the stage of physical ripening or grain preparation, for example, using cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt, etc. May be.

The silver halide photographic light-sensitive material of the present invention comprises
Various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include (RD) No. 17643 and (RD) No. 18 described above.
Various compounds described in 716 and (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page 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 26-27 XI 650 Right 1005-6 XI 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 RD above. Suitable supports include polyethylene terephthalate, and the support surface is a coating layer. In order to improve the adhesiveness, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be performed.

The development processing method of a silver halide light-sensitive material according to the present invention includes steps from development to drying when processed by an automatic processor including the steps of development, fixing, washing (or stabilizing) and drying. It is preferably completed within 90 seconds.

That is, the time from the time when the tip of the photosensitive material starts to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing steps (so-called Dry to Dry time).
Within 90 seconds, more preferably this Dry to
The dry time is within 60 seconds.

[0056]

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

Example 1 [Preparation of Emulsion 1] 1) Preparation of seed emulsion 1 2 mol of silver iodide having an average grain size of 0.3 μm by a double jet method while controlling 60 ° C., pAg = 8 and pH = 2.0. % Monodisperse cubic crystal grains of silver iodobromide were prepared. The obtained reaction solution was desalted at 40 ° C. using an aqueous solution of Demol N and an aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then an aqueous solution of gelatin was added and redispersed to obtain a seed emulsion.

2) Growth from Seed Emulsion 1 Using the above seed emulsion, grains were grown as follows. First, disperse the seed emulsion in a gelatin aqueous solution kept at 40 ° C,
Further, the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous ammoniacal silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added to this solution by the double jet method. During the addition, the pH was controlled to 7.3 and the pH to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method.
Keep pAg = 9.0 up to 95% of the target particle size, and pH from 9.0 to 8.
It was continuously changed to 0. After that, the pH was adjusted to 11.0, and the grain size was grown to the target grain size while maintaining pH = 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid, and 400 mg / mol AgX of 5,5′-dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydride was added. After desalting with an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, an aqueous gelatin solution was added and redispersed.

By this method, the average silver iodide content was 1.0 mol%, and the vertices were rounded and the average grain size was 0.40 μm and 1.0.
Monodisperse silver iodobromide emulsions (A) and (B) having 0 μm and variation coefficients (σ / r) of 0.17 and 0.16 were prepared.

[Preparation of Emulsion 2] 1) Preparation of Seed Emulsion 2 Including hydrogen peroxide-treated gelatin vigorously stirred at 40 ° C.
To the 0.05N potassium bromide aqueous solution, an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin was added by the double jet method, and 1.5 minutes later
After lowering the liquid temperature to 5 ° C., 80 ml of ammonia water (28%) was added per mol of silver nitrate, and stirring was continued for 5 minutes. Then, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then an aqueous gelatin solution was added and redispersed. The resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

2) Growth from Seed Emulsion 2 Using the above seed emulsion, grains were grown as follows. 75
To an aqueous solution containing ossein gelatin and propyleneoxy / polyethyleneoxydisuccinate / disodium salt vigorously stirred at ℃, an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method. During this period, pH was kept at 5.8 and pH was kept at 9.0. After the addition is complete,
Adjusted to 6.0, 5,5'-dichloro-9-ethyl-3,3'-di- (3-
Anhydrous of sulfopropyl) -oxacarbocyanine sodium salt was added at 400 mg / mol AgX.

Further, after desalting at 40 ° C. with an aqueous solution of Demol N and an aqueous solution of magnesium sulfate manufactured by Kao Atlas, an aqueous gelatin solution was added and redispersed.

By this method, a tabular silver iodobromide emulsion (C) having an average silver iodide content of 0.5 mol% and a projected area diameter of 0.55 μm, a coefficient of variation of 0.25 and an aspect ratio of 4.0 was prepared.

[Preparation of Sample] The obtained emulsion (A),
(B), (C) and four emulsions obtained by the preparation 2 of the seed emulsion prepared as (D) were added with the exemplary spectral sensitizing dyes II-2 and III-5 at a temperature of 55 ° C. It was added at a weight ratio of 200: 1 in the amounts shown in Table 1.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added 3 × per mol of silver halide. 10 ^-2 mol was added and dispersed in an aqueous solution containing 70 g of gelatin.

The following additives were added to each of the obtained emulsions. The addition amount is shown as the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butylcatechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1, Ammonium 3-dihydroxybenzene-4-sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg 1-Phenyl-5-mercaptotetrazole 10 mg Trimethylolpropane 10 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N ( CH ₂ COOH) ₂ 1 g

[0068]

[Chemical 10]

The additives used in the protective layer liquid are as follows. The added amount is shown as an amount per 1 l of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate Matt agent having an area average particle size of 3.5 μm 1.1 g Silicon dioxide particles Area average particle size of 1.2 μm Matting agent 0.5 g Ludox AM (made by DuPont) (colloidal silica) 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 500 mg C ₁₂ H ₂₅ CONH ( CH ₂ CH ₂ O) ₅ H 2.0 g

[0071]

[Chemical 11]

Preparation of subbed base: Polyethylene terephthalate base having a thickness of 175 μm and colored in blue.
Methyl acrylate 10wt%, Butyl methacrylate 40wt
% Of a copolymer of 3 types of monomers, the concentration of which is 10
The copolymer aqueous dispersion obtained by diluting the mixture so as to be wt% was applied as an undercoat liquid.

Preparation of base with mordant layer A mordant layer composed of the following compounds was coated on the base having the above-mentioned undercoat layer.

[0074]

[Chemical 12]

For each of the obtained emulsions, the one closer to the base was set as the emulsion first layer and the farther one was set as the emulsion second layer on the above two types of bases, and the silver coating amount and gelatin coating as shown in Table 1 were used. The coating liquid was prepared by adjusting the amount.

The surface protective layer has a gelatin coating amount of 1.
It was adjusted to 0 g / m ² and both slide hopper type coaters were used to simultaneously coat both sides of the emulsion layer (emulsion 1st and 2nd layers) and the protective layer at a speed of 90m / min for 2 minutes 15 seconds. Dried in.

Development processing and evaluation Development processing was carried out using a roller-conveying type automatic developing machine SRX-503, and a developing solution and a fixing solution were SR-DF (both manufactured by Konica Corporation) at a developing temperature of 36.5 ° C. and a fixing temperature of 33 ° C. The entire treatment process was carried out at a water washing temperature of 18 ° C for 30 seconds (the SRX-503 was modified to allow the line speed to be changed for 30 seconds), and the following items were evaluated.

Sensitivity The obtained sample was sandwiched between two fluorescent intensifying screens HG-M (manufactured by Fuji Photo Film Co., Ltd.) and irradiated with X-ray for 0.05 seconds at a tube voltage of 90 kVP and a tube current of 20 mA through an aluminum wedge. Then, a sensitometric curve was created by the distance method to determine the sensitivity and the maximum density (Dmax).

The sensitivities in the table are relative sensitivities when the sample No. 1 is set to 100, which is obtained as the reciprocal of the X-ray dose required to obtain the density of fog + 1.0.

Sharpness The obtained sample was sandwiched between fluorescent intensifying screens HG-M, irradiated with X-rays at a tube voltage of 90 kVP, a rectangular wave chart was measured, and MTF was determined by the contrast method. MTF is spatial frequency 2.0L
The value of P / mm is shown. The higher the value, the better the sharpness of the image.

Color Remaining Property The obtained sample was processed under the above-mentioned development conditions without being exposed,
The transmission density of the treated sample was measured with green light. The smaller the value is, the less the residual color contamination is and the better.

Development silver color tone The obtained sample was exposed to a transmission density of 1.2 after development, and then developed using the above-mentioned automatic processor. Observing the developed sample obtained on Schaukasten,
The silver tone due to transmitted light was visually evaluated according to the following criteria.

1: Pure black tone 2: Slightly reddish black 3: Slightly yellowish black 4: Yellowish black The above results are shown in Table 1 below.

[0084]

[Table 1]

As is clear from the table, the sample according to the present invention gave an image having excellent sharpness and little residual color.
Further, the developed silver tone was pure black tone and had high sensitivity.

[0086]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has no residual color contamination even after rapid processing, has excellent image sharpness, and can obtain a pure black tone of image silver. .

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least two silver halide emulsion layers on at least one side of a support, the silver halide emulsion layer being closest to the support. The amount of the spectral sensitizing dye used is 2.0 mg or more and 7.0 mg / m ² or less per side, and the amount of the spectral sensitizing dye contained in the silver halide emulsion layer farthest from the support is 7.5 mg per side. A silver halide photographic light-sensitive material for X-rays, characterized by having an amount of mg / m ² or more.