JPH04296845A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To improve a color tone of a silver image and prevent soft gradation caused by mixing of a developer into a fixer. CONSTITUTION:In a photosensitive material having two or more silver halide emulsion layers respectively on both sides of a carrier, a dyestuff having an absorption maximum at 520-560nm and/or another dyestuff having that at 570-700nm are contained in emulsion layers other than the outermost emulsion layers and, if required, a phenylmercaptotetrazole compound is contained in the outermost emulsion layers.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and in particular, it has improved blackness of image silver, high sensitivity, high covering power, and suitability for mixing with a fixer. The invention relates to an excellent photographic material.

0002

BACKGROUND OF THE INVENTION The covering power of silver halide emulsions is of great interest to manufacturers of sensitive materials. The reason for this is that using a high covering power emulsion saves on the amount of silver needed to maintain a constant optical density. U.S. Pat. No. 4,411,98 shows that the use of a tabular emulsion with a high aspect ratio and small grain thickness significantly increases the developed silver coverage.
No. 6, No. 4,434,226, No. 4,413,0
It is disclosed in No. 53, etc. Furthermore, JP-A-58-10
No. 8,526 discloses that extremely high photosensitivity and covering power can be obtained by so-called epitaxial tabular grains in which another silver salt is placed at a specific location on a tabular grain with a high aspect ratio and a small grain thickness. . In addition to the above-mentioned emulsions, high-sensitivity fine-grain emulsions with small average grain sizes and high-sensitivity tabular grain emulsions with small average grain thicknesses have higher silver covering power than emulsions with larger average grain sizes and average grain thicknesses. is well known.

However, the color tone of the developed silver of the emulsion grains that provide the above-mentioned high silver covering power is yellowish, which almost always depends on the grain size and grain thickness, giving an unpleasant impression to the image viewer. This yellowish tinge is due to the fact that as the particle size and thickness decrease, the size and thickness of the developed silver also decreases, and the scattering of blue light components increases, resulting in light with a strong yellowish tinge. This phenomenon is a particular problem when fine grain emulsions (for example, average grain size of 0.4 μm or less) or thin tabular grains (for example, grain thickness of 0.4 μm or less) are used as silver halide emulsions. Become.

0004

[Problems to be Solved by the Invention] The object of the present invention is to provide a silver halide photosensitive material which has high sensitivity and high covering power and has improved blackness of image silver, and furthermore, it is an object of the present invention to provide a silver halide photosensitive material which has high sensitivity and high covering power and which has improved blackness of image silver. An object of the present invention is to provide a silver halide photosensitive material which prevents the softening that sometimes occurs and improves the blackness of image silver. As a means of improving the color tone of image silver, a method of adding a color tone adjusting dye to the emulsion layer was disclosed in JP-A-62-2.
No. 76539, JP-A No. 2-297539, etc. Although these techniques do improve the color tone of developed silver, it has become clear that they cause unexpected drawbacks. One is that the pressure resistance of the sensitive material has deteriorated significantly, and the other is that phenylmercaptotetrazole compounds, which have the effect of preventing softening when a small amount of fixer is mixed into the developer, are added to the emulsion layer. When added, it caused significant desensitization over time at high humidity.

[0005]

[Means for Solving the Problems] The present inventor has solved the above problem by solving a silver halide emulsion layer that is not the uppermost layer when viewed from the support in a sensitive material having two or more silver halide emulsion layers on both sides of the support. It has been found that this problem can be solved by containing a dye for color tone adjustment in at least one layer of the above. The reason for the improvement is not clear, but it is thought that it is because pressure resistance deteriorates when the color tone adjusting dye comes into contact with the uppermost surface protective layer. Furthermore, in the processing of sensitive materials with improved color tone, when a small amount of the fixer mixes with the developer, the gradation changes and becomes softer. It has been found that by adding it to the layer, it is possible to prevent softening of the tone without causing desensitization over time under high humidity. The dye used in the present invention has a wavelength of 520 to 560 nm, preferably 53 nm.
dyes with maximum absorption wavelength between 0 and 555 nm, and/or between 570 and 700 nm, preferably between 580 and 650 nm;
It is a dye with a maximum absorption wavelength between nm. Here, the maximum absorption wavelength exhibited by the dye in the present invention means the maximum absorption wavelength when the dye is present in the light-sensitive material. Dyes preferably used in the present invention include, for example, anthraquinone dyes, azo dyes, azomethine dyes, indoaniline dyes, oxonol dyes, carbocyanine dyes,
A dye having a predetermined maximum wavelength is selected from among styryl dyes, triphenylmethane dyes, etc. In consideration of the stability to development, light fastness, desensitization, fogging, staining, and other effects on photographic performance, anthraquinone dyes, azo dyes, azomethine dyes, and indoaniline dyes are preferably used. More preferably,
Dyes represented by the following general formulas (I) and (II) are used.

[0006]

[Chemical formula 1]

In the formula, R11, R12 and R21 may be the same or different and each represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, R13, R24 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R14, R15, R2
5 and R26 may be the same or different and each represents a substituted or unsubstituted alkyl group (R14 and R15 or R25 and R26 may be linked to each other to form a ring), R22 is a hydrogen atom, represents an alkyl group or a halogen atom, R23 represents a hydrogen atom, an alkyl group or an acylamino group (R22 and R23 may be linked to each other to form a ring), Z11 is -NHCO
-, -NH-, -NHCONH-, -COO- or -
represents O-, and Z21 represents -CONH-, -NHCO- or -NHCONH-. n represents 0 or 1. Specific examples of dyes represented by general formulas (I) and (II) are illustrated below.

[0008]

[Case 2]

[0009]

[Chemical formula 3]

In addition to the above-mentioned dyes, dyes used in the present invention include, for example, dye N described in JP-A No. 62-276539.
o. 1~No. 45, JP-A No. 2-297539, pages 328 to 332. In the present invention, the dye content is such that the density increase due to the dye content in the transmission density of the unexposed area after the development process is 0.
03 or less, and the color tone at a density of 1.0 is neutral black. However, the optimum amount of dye to be added depends on the support concentration, the extinction coefficient of the dye, the maximum absorption wavelength of the dye, and the color tone of the developed silver. and the ratio of addition amount of 520-560 nm dye and 570-700 nm dye is also similar, but the addition amount of each is from 1 x 10-7 mol/m2 to 1 x
Preferably, 10-4 mol/m2 is used. More preferably from 2 x 10-7 mol/m2 to 2 x 10-5 mol/m
2, most preferably 5 x 10-7 mol/m2
to 1.5 x 10-5 mol/m2. The method of adding the dye of the present invention is disclosed in JP-A-62-276539 No. 31.
The method described on pages 1 to 313 can be used.

The photosensitive material of the present invention has two layers on each side of the support.
It has more than one photosensitive silver halide emulsion layer. The weight ratio of Ag to binder, sensitivity, silver halide grain shape, halogen composition, and coating amount of silver in each emulsion layer are arbitrary. However, it is preferable that the contribution of the amount of coated silver in each emulsion layer to the total amount of coated silver is 25% or more, the Ag/binder ratio is 2.0 or less, and the amount of coated silver on one side is 3 g/m2 or less.

Typical examples of the compounds used in the uppermost emulsion layer of the present invention are shown in Table 1.

[0013]

[Table 1]

The desirable amount of these compounds added to the amount of silver in the uppermost emulsion layer is 5 x 10-3 mol to 5 x 10-3 mol.
5 moles/1 mole silver. These compounds can be used in suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methylcellosolve, JP-A-48-97
It can be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, water, etc. or a mixed solvent as described in No. 15 and US Pat. No. 3,756,830.

Preferred silver halide emulsion grains used in the present invention include tabular silver halide grains and cubic, octahedral, tetradecahedral, and spherical silver bromide and iodine grains having an average equivalent grain size of 0.5 μm or less. Examples include silver oxide and silver chlorobromide particles. When forming these grains, a method of converting the surface and/or interior by adding a less soluble halogen is useful for obtaining a highly sensitive silver halide emulsion. The tabular silver halide emulsions preferably used in the present invention are described in JP-A-62-276539, pages 311 to 313, and JP-A-2-68539, page 8, lines 6 to 10 from the bottom of the upper right column. The description on the 12th line in the upper right column of the page can be referred to.

[0016] There are no particular limitations on the various other additives, developing methods, and other techniques used in the photosensitive material of the present invention, and for example, those described in the following relevant sections of JP-A No. 2-68539 can be used. . Item
Applicable location 1.
Chemical sensitization method JP-A-2-6853
Publication No. 9, page 10, upper right column, line 13
Line 16 in the lower left column from the eye. 2. Antifoggant/Safety, page 10, bottom left column 1
From line 7 to page 11, top left column 7 Fixing agent
line and page 3, lower left column 2
From line 4, bottom left column of the same page
. 3. Spectral sensitizing dyes From line 4 in the lower right column of page 4 to lower right column of page 8. 4. Surfactant/Electrostatic page 11, top left column 1
From line 4 to page 12, top left column 9 Inhibitor
Row number. 5. Matting agent/Sliding agent/Page 12, top left column 10
From line 10 to line 10 in the upper right column. Plasticizer Page 14, line 10 in the lower left column to line 1 in the lower right column. 6. Hydrophilic colloids, page 12, line 11 of the upper right column to line 16 of the lower left column of the same page. 7. Hardener No. 12
From line 17 in the lower left column of the page to page 6 in the upper right column of page 13
Row number. 8. Support No. 13
Lines 7 to 20 in the upper right column of the page. 9. Dyes and mordants From page 13, lower left column, line 1 to page 14, lower left column, line 9
eye. 10. Development processing method JP-A-2-1
Publication number 03037, page 16, upper right column, line 7
19th from the eyes
Line 15 in the bottom left column of the page. and JP-A-2-
Publication No. 115837, page 3, lower right column, line 5 to line 6
Top right column, line 10 of the page. The photographic light-sensitive material of the present invention is mainly used as a medical direct X-ray light-sensitive material, but its use is not limited thereto.

[0017]

Examples Example 1 (1) Preparation of dye emulsion dispersion Preparation of magenta emulsion Dye Dye Example No. 7 and 0.01 g of the following oligomer surfactant were dissolved in 3 cc of ethyl acetate, added to 15 cc of an aqueous gelatin solution (15 wt%), and stirred at high speed at 15,000 rpm with a homogenizer to emulsify and disperse. The maximum absorption wavelength of the obtained emulsion was 545 nm.

Preparation of Cyan Emulsion A cyan emulsion was obtained in exactly the same manner as for the magenta emulsion described above, except that 0.2 g of the following cyan dye was added instead of the magenta dye. The maximum absorption wavelength of the emulsion was 620 nm.

[0019]

[C4]

(2) Preparation of surface-sensitive silver halide emulsion Preparation of emulsion-a In 1 liter of water, 5 g of potassium bromide, 0.05 g of potassium iodide,
30g gelatin, thioether HO(CH2)2
2.5 cc of a 5% aqueous solution of S(CH2)2S(CH2)2 OH was added to the solution kept at 73°C, and with stirring, 8.33 g of silver sulfate aqueous solution and 5.94 g of potassium bromide were added.
, and an aqueous solution containing 0.726 g of potassium iodide were added in 45 seconds by a double jet method. Next, potassium bromide 2.5
After adding 2 g of silver nitrate, 2 g of an aqueous solution containing 8.33 g of silver nitrate was added.
The mixture was added over a period of 6 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition. After this, 25% ammonia solution 2
0cc, adding 10cc of 50% NH4NO3
After physical aging for 0 minutes, 240 cc of 1N sulfuric acid was added to neutralize. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 40 minutes by a controlled double jet method while maintaining the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate at the end of addition was nine times the flow rate at the start of addition. At the end of the addition, 15 cc of 2N potassium thiocyanate solution was added, and then 55 cc of 1% aqueous potassium iodide solution was added over 30 seconds. After that, the temperature was lowered to 35°C and soluble salts were removed by a sedimentation method, and then the temperature was raised to 40°C, 30g of gelatin and 2g of phenol were added, and the pH was adjusted to 6.0 with caustic soda and potassium bromide.
40, pAg was adjusted to 8.10. After raising the temperature to 56° C., 600 mg of a sensitizing dye having the following structure and 150 mg of a stabilizer were added. After 10 minutes, 2.4 mg of sodium thiosulfate pentahydrate, 140 mg of potassium thiocyanate, and 2.1 mg of chloroauric acid were added to each emulsion, and after 80 minutes, the emulsions were rapidly cooled and solidified to form an emulsion. In the obtained emulsion, 98% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 1.4 μm, standard deviation 15%, and thickness. The average was 0.187 μm and the aspect ratio was 7.5.

[0021]

[C5]

Preparation of Emulsion-b In 1 liter of water, 3.5 g of potassium bromide, 0.05 g of potassium iodide, 30 g of gelatin, thioether HO (CH
2)2S(CH2)2S(CH2)2OH
1.8 cc of a 5% aqueous solution of was added and kept at 73°C, and while stirring, an aqueous solution of 8.33 g of silver sulfate and an aqueous solution containing 5.94 g of potassium bromide and 1.00 g of potassium iodide were added. It was added in 45 seconds by jet method. Subsequently, 2.5 g of potassium bromide was added, and then an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition. After this, 20 cc of 25% ammonia solution and 10 cc of 50% NH4 NO3 were added, and after physical aging for 20 minutes, 240 cc of 1N sulfuric acid was added.
It was neutralized by adding c. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 40 minutes by a controlled double jet method while maintaining the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate at the end of addition was nine times the flow rate at the start of addition. At the end of the addition, 15 cc of 2N potassium thiocyanate solution was added, and then 55 cc of 1% aqueous potassium iodide solution was added over 30 seconds. After this, increase the temperature to 3
After lowering the temperature to 5°C and removing soluble salts by the sedimentation method,
The temperature was raised to 40℃, 30g of gelatin and 2g of phenol were added, and the pH was adjusted to 6.40 and pAg with caustic soda and potassium bromide.
Adjusted to 8.10. After raising the temperature to 56° C., 600 mg of a sensitizing dye having the following structure and 150 mg of a stabilizer were added. After 10 minutes sodium thiosulfate pentahydrate2.
4mg, potassium thiocyanate 140mg, chloroauric acid 2.1
mg was added to each emulsion, and after 80 minutes, it was rapidly cooled and solidified to form an emulsion. In the obtained emulsion, 98% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 1.2μ, standard deviation 18%, and thickness. The average of is 0.1
The aspect ratio was 7.0 at 71 μm.

[0023]

[C6]

Preparation of Emulsion Coating Solution/Emulsion Layer First Layer-(a) The following chemicals were added per mole of silver halide to Emulsion-a to prepare a coating solution.・Gelatin Ag/gelatin (weight ratio)
Adjust the amount added so that it becomes 1.3 ・Polymer latex (poly(ethyl acrylate/methacrylate)
acid)=97/3)

25.0g ・1,2-bis(sulfonylacetamide) ethane
*Swelling rate should be 230%

Adjust the amount added to

[0025]

[C7]

・2,6-bis(hydroxyamino)-4-
Diethylamino-1,3,5-triazid
hmm

80mg ・Sodium polyacrylate (average molecular weight 41,000)

4.0g
・Potassium polystyrene sulfonate (average amount
molecular weight 600,000)

1.0g

*Measurement of swelling ratio: (a) Incubating the photographic material at 38°C and 50% relative humidity for 3 days; (b) measuring layer thickness; and (c) placing the photographic element in water at 21°C. Determined by soaking for 3 minutes and (d) measuring the percentage change in layer thickness compared to the layer thickness measured in step (b).

Emulsion layer 1st layer - (b) Emulsion layer
1st layer - (a) Magenta emulsion magenta dye 2.4 x 10-5 mol/mol Ag
Cyan emulsion cyan dye 1.2 x 10-4 mol/mol A
g was added to form the first emulsion layer (b).

Emulsion layer 2nd layer-(a) Emulsion-b
The following chemicals were added per mole of silver halide to prepare a coating solution.・Gelatin Ag/gelatin
Adjust the amount added so that it is 1.5 ・Polymer latex (poly(ethyl acrylate/methacrylate)
acid) = 97/3)

25.0g

[0030]

[Chemical formula 8]

・2,6-bis(hydroxyamino)-4-
Diethylamino-1,3,5-triazid
hmm

80mg ・Sodium polyacrylate (average molecular weight 41,000)

4.0g
・Potassium polystyrene sulfonate (average amount
molecular weight 600,000)

1.0g ・Magenta emulsion Magenta dye
4.8×10-5 mol/mol Ag ・Cyan emulsion Cyan dye
2.4×10-4 mol/
Mol Ag

- Emulsion layer 2nd layer - (b) 2nd layer
Based on the composition of layer (A), the amounts of magenta and cyan dyes added were changed as follows. magenta dye
2.4 x 10-5 mol/mol Ag cyan dye
1.2×10-4
Mol/mol Ag This is the second layer (b).

Preparation of surface protective layer coating solution The surface protective layer was prepared so that each component was coated in the following amounts. Contents of surface protective layer

Application amount/gelatin

0.966g/m2・Sodium polyacrylate (average molecular weight
0.023 400,000) ・4-hydroxy-6-methyl-1,3,
0.015 3a,7
-tetrazaindene

[0034]

[Chemical formula 9]

- Polymethyl methacrylate (average particle size
0.087 3.7
μm) ・Proxel

0.0005 (adjusted to pH 7.4 with NaOH)

The above emulsion coating solution and the surface protective layer coating solution were coated on both sides of a blue-colored polyethylene terephthalate support having a thickness of 180 μm so that the amount of silver coated on each side was 1.8 g/m 2 . Photosensitive materials -1 and -2 were prepared as shown in Table 2.

[0037]

[Table 2]

Evaluation of Pressure Properties Photosensitive material-1 (invention) and photosensitive material-2 (comparison) were each folded at a bending angle of 25°. Thereafter, the sample was exposed to light using a sensitometer, and was subjected to dry-to-dry processing for 45 seconds using an X-ray processor manufactured by Fuji Photo Film Co., Ltd. and using processing liquid RD-7 also manufactured by Fuji Photo Film Co., Ltd. In Photosensitive Material-1 of the present invention, almost no desensitization was observed in the folded portion, but in Comparative Sample Photosensitive Material-2, the density at the folded portion was lower than the surrounding density and was desensitized.

Example 2 Preparation of Photosensitive Material-3 The following compound (A) was added to the first emulsion layer (A) at 5×10 −4
A photosensitive material-3 was prepared having the same composition as the photosensitive material-1 except that mol/mol of Ag was added.

[0040]

[Chemical formula 10]

Further, 5×10 − of the above compound (a) was added to the first emulsion layer (b) and the second emulsion layer (b), respectively.
Photosensitive material-4 was prepared using the same composition as photosensitive material-2 except that 4 mol/mol of Ag was added.

Evaluation of photographic properties when a small amount of fixer is mixed in the developer The photographic materials RD-7 and RD-7 as in Example 1 were used as the post-processing solution after exposing the light-sensitive materials -1 to -3 with a wedge using a sensitometer. D
A dry to dry process was performed for 45 seconds.

The results are shown in Table 3.

[0044]

[Table 3]

It can be seen that the degree of gradation softening in Photosensitive Materials -3 and -4 is small even when the developer is mixed with a fixer. In addition, the results of the same 25° bending test as in Example 1 showed that the photosensitive material -
Similar to Photosensitive Material-1, Sample No. 3 showed almost no signs of desensitization at the folded portion.

Evaluation of wet desensitization over time After leaving the photosensitive materials -1 to -4 under the condition of 30° and 80% for 4 days, the sensitivity was 1/20 with a sensitometer along with the fresh photosensitive materials -1 to -4.
Wedge exposure was performed in seconds and the difference in sensitivity was investigated. Processing is done by automatic processing machine F
PM-9000 and treatment liquid RD-7. The results are shown in Table 4.

[0047]

[Table 4]

Photosensitive materials-1 and -3 of the present invention have almost no desensitization due to bending, and photosensitive material-3 is wet.
It can be seen that the blackness of the image silver is improved because there is little thermo-desensitization and the gradation softening caused by the developer mixed with the fixer is small.

[0049]

Effects of the Invention The present invention provides a silver halide sensitive material having two or more emulsion layers on both sides of a support, in which dyes and/or dyes having an absorption wavelength of 520 to 560 nm are added to emulsion layers other than the outermost emulsion layer. By incorporating a dye having an absorption wavelength in the range of 570 to 700 nm, it was possible to improve the tone of the silver image and prevent the softening that occurs when the fixer is mixed into the developer.

Claims (2)

[Claims] Claim 1: In a silver halide photographic material having two or more photosensitive silver halide emulsion layers on each side of a support, at least one of the emulsion layers other than the uppermost emulsion layer when viewed from the support. The layer contains a dye with a maximum absorption wavelength between 520 and 560 nm and/or between 570 and 700 nm.
1. A silver halide photographic material comprising a dye having a maximum absorption wavelength between 1 and 2. 2. The silver halide photographic material according to claim 1, wherein the uppermost emulsion layer viewed from the support contains a phenylmercaptotetrazole compound.