JPH05313268A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a diagnostic silver halide photosensitive material superior in graininess and sharpness and less in pressure fog and black scratches. CONSTITUTION:This silver halide photographic sensitive material to be used for diagnostic service has at least each one silver halide emulsion layer and each one hydrophilic colloidal layer on both sides (A, B) of a support, and sensitivity SA and gradation gammaA on the side A and sensitivity SB' on the side B, when it is exposed from only the side A, and sensitivity SB and gradation gammaB on the side B, and sensitivity SA' on the side A, when it is exposed only from the side B, have the following relationships: [I] SA/SA' >4.0, [II] SA/SB=0.8-1.5, and [III] gammaB/gammaA >1.1. The silver to gelatin weight ratio in the emulsion layer on the side A is smaller than that on the side B.

Description

Detailed Description of the Invention

[0001]

The present invention has excellent graininess and sharpness,
The present invention also relates to a silver halide photographic light-sensitive material for medical use, which is less susceptible to scratches and blackening caused by pressure when handling the film.

[0002]

2. Description of the Related Art Recently, as a silver halide photographic light-sensitive material for medical use, a light-sensitive material having high sensitivity, high latitude, excellent graininess, high sharpness and suitability for rapid processing has been required. For these requirements, for example, Japanese Patent Laid-Open No. 4-102843,
A No. 3-28842, No. 2-266344
A double-sided emulsion-coated silver halide light-sensitive material having different sensitivities and gradations on the surface B and the surface B is disclosed. Furthermore, with the increasing need for rapid processability in recent years, it has excellent granularity and sharpness in order to accurately detect fine lesions and improve diagnostic ability, and scratches caused by pressure during handling of the film The development of few technologies was strongly desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a medical silver halide photographic light-sensitive material having excellent graininess and sharpness, less scratches when the film is handled, and improved diagnostic ability. That is.

[0004]

The above object has been achieved by the following constitution. That is, both sides of the support (each A
Surface, referred to as surface B), and a hydrophilic silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer on the surface A when exposed only from the surface A side. Sensitivity is SA, gradation is γA, and sensitivity on the B side is S
Supposing that B'is the sensitivity of the B side when exposed from the B side only, SB is the gradation, and SA 'is the sensitivity of the A side, SA, SB, SA', SB'γA, γB Are in the relationship represented by the following formulas [I], [II] and [III], and [I] SA / SA '> 4.0 [II] SA / SB = 0.8 to 1.5 [III] γB /ΓA>1.1 and the silver (A) / gelatin (A) (weight) ratio of the emulsion layer on the A side is smaller than the silver (B) / gelatin (B) (weight) ratio of the emulsion layer on the B side. A silver halide photographic light-sensitive material characterized by the above. Here, the sensitivity is base density + fog density + 1.
The reciprocal of the exposure amount required to obtain the density of 0 is obtained, and S
A, SB, SA ', SB'. The gradation is the average gradation made by base density + fog density + 0.3 and base density + fog density + 0.8 in the characteristic curve on the Cartesian coordinates with the same unit axis length of logarithm of optical density and exposure amount (log E). Stipulate in.

Exposure for determining sensitivity and gradation is performed as follows. Exposure condition -1 Fluorescent intensifying screen used (depending on the photosensitive wavelength of the film used) (a) In the case of a photosensitive material (regular) having sensitivity in the blue region, one containing CaWO ₄ as a main component (for example, Fuji Photo Film ( (Hi-Screen series manufactured by K.K.) (a) In the case of a sensitive material (ortho) having sensitivity in the green region, one containing Gd ₂ O ₂ S activated by Tb as a main component (for example, Fuji Photo Film ( HR series manufactured by K.K.)-2 X-ray irradiation conditions Tube voltage: 70kV Grid: Unused Tube current: 100mA Time: 0.1sec Distance: 1.85m-3 Exposure method Put an intensifying screen only on the back side of the cassette. , And after stacking the sample (film) on it, through the aluminum stage
Exposure is performed under the condition of 2.

Development developer and fixer CE-D-F1 (manufactured by Fuji Photo Film Co., Ltd.) Development temperature 35 ° C., fixer temperature 32 ° C. Development machine CEPROS M (Fuji Photo Film Co., Ltd.)
Sensitivity and gradation measurement method Regarding the developed sample, the sample exposed only from the A side is divided into two, one is SA, the B side is removed for γA measurement, and the other is A for SB ′ measurement. Remove the face. Then B
Also for the sample exposed only from the surface, the surfaces A and B are similarly removed for measuring SB, γB and γA ′, respectively. The sensitivity of the silver halide photographic light-sensitive material according to the present invention on the A and B sides is SA / SA '> 4.0, preferably 5.0 or more, S
A / SB = 0.8 to 1.5, preferably 0.8 to 1.3
Is to be. The gradation ratio is γB / γA> 1.1, preferably 2.5> γB / γA> 1.2.

SA / SA '> 4.0, SA / SB =
In order to achieve 0.8 to 1.5 and γB / γA> 1.1, the emulsion contained in the emulsion layer on the A side needs to have higher sensitivity than the emulsion on the B side. In order to achieve high sensitivity, means such as increasing the grain size of silver halide grains, increasing the efficiency of chemical sensitization, and increasing the efficiency of spectral sensitization are required. Adopting such a sensitizing means remarkably increases the blackening of scratches caused by pressure when the film is handled. Further, in recent years, high-temperature rapid processing has rapidly spread in the development process of photographic light-sensitive materials, and the processing time thereof has been greatly shortened even in the processing of automatic developing machines for various photosensitive materials. Improvements in emulsion technology and film quality technology are necessary to enable rapid high-temperature processing, and among these, reduction in the amount of hydrophilic coating binder is a major technology for achieving rapid processing and rapid drying.

However, when the amount of the hydrophilic binder in the emulsion layer is reduced and the silver / binder ratio is increased, the scratch blackening becomes remarkable. SA / SA '> 4.0, SA / SB =
In the light-sensitive material of the present invention having excellent sharpness and graininess satisfying the conditions of 0.8 to 1.5 and γB / γA> 1.1, the light-sensitive material of the present invention has rapid processability and less scratch blackening during handling. In order to achieve this, the relationship between the silver / gelatin ratios of A-side and B-side is such that silver (A) / gelatin (A) <silver (B) / gelatin (B) (weight ratio) is satisfied and the total amount of hydrophilic binder is It has been found desirable to reduce.

At this time, the total amount of hydrophilic binder on the A side is B
It is desirable not to be less than the total hydrophilic binder amount on the surface. The hydrophilic binder in the present invention means a hydrophilic colloid substance such as gelatin, a natural or synthetic hydrophilic polymer. In the present invention, the weight ratio of silver to gelatin is in the range of silver / gelatin ≧ 0.5, preferably 4.0 ≧ silver / gelatin ≧ 0.6, particularly preferably 3.0.
≧ Silver / gelatin ≧ 0.8 is preferred.

There are no particular restrictions on the various additives and the like used in the photographic light-sensitive material of the present invention. For example, those described in the following relevant parts can be used. Item This section 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, lower column, 6 from its manufacturing line to 10th page, upper right column, 12th column, 3-245 37 Gazette, page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11, lower left column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggant, stability JP-A-2-68539, page 10, lower left column, line 17 Agents to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column .. 4) Color improver JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 5) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 7) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 Plasticizer to the same upper right column, line 10; page 14, lower left column, line 10 to right lower column, line 1

8) Hydrophilic Colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 9) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 10) Supports JP-A-2-68539, page 13, upper right column, lines 7 to 20. 11) Crossover JP-A-2-264944, page 4, upper right column, line 20: From cut method, page 14, upper right column. 12) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24537, page 14, lower left column to page 16, lower right column. 13) Polyhydroxy JP-A-3-39948, page 11, upper left column to benzenes, page 12, lower left column, EP Patent No. 452772A. 14) Layer structure JP-A-3-198041. 15) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10

[0012]

EXAMPLES The present invention will be specifically described. Example 1 Preparation of Emulsion-A 5 g of potassium bromide and 0.05 g of potassium iodide in 1 liter of water,
Gelatin 30g, thioether _{HO (CH 2) 2 S (} CH 2) 2 S (CH 2) 2
Add 3.5 cc of 5% aqueous solution of OH, and while stirring, add an aqueous solution of 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide while stirring. It was added by the jet method in 45 seconds. 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 addition was twice that at the start of addition. After that, 20 cc of 25% ammonia solution and 10 cc of 50% NH ₄ NO ₃ were added to give 20
After physical aging for 15 minutes, 15 cc of glacial acetic 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 by the control double jet method for 40 minutes while keeping the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate at the start of addition was 9 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 further 25 cc of 1% potassium iodide aqueous solution was added over 30 seconds. After this, the temperature is 35 ℃
After removing the soluble salts by sedimentation method,
The temperature was raised to 30 ° C., 30 g of gelatin and 2 g of phenol were added, and the pH was adjusted to 6.40 with sodium hydroxide and potassium bromide.
Adjusted to 50. After the temperature was raised to 56 ° C., 520 mg of sensitizing dye A having the following structure and 150 mg of stabilizer A were added. After 10 minutes, sodium thiosulfate pentahydrate 2.4 m
g, potassium thiocyanate 140 mg, chloroauric acid 2.1 mg
Were added, and after 80 minutes, they were rapidly cooled and solidified to give emulsions. In the obtained emulsion, 98% of the total projected area of all grains was composed of grains having an aspect ratio of 3 or more, and the average projected area diameter of all grains having an aspect ratio of 3 or more was 1.6.
The average thickness was 0.2 μm, and the aspect ratio was 8.0.

[0013]

[Chemical 1]

Preparation of Emulsion-B In the preparation of Emulsion-A, the thioether HO (CH ₂ ) ₂ S (CH ₂ )
Emulsion-Emulsion-A exactly the same as emulsion-A, except that the amount of 5% aqueous solution of ₂ S (CH ₂ ) ₂ OH was 2.4 cc and the preparation temperature was 72 ° C.
B was obtained. The average projected area diameter is 1.4 μm and the standard deviation is 15 for all grains with an aspect ratio of 3 or more.
%, And the aspect ratio was 7.4.

Preparation of Emulsion-C In the preparation of Emulsion-A, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S
(CH ₂ ) ₂ OH 5% aqueous solution added amount 2.0cc Charge temperature 6
9 ° C, 25% ammonia solution 15cc, glacial acetic acid 11.5c
Emulsion-C was prepared in the same manner as in Emulsion-A, except that the amount of sensitizing dye A was 600 mg, sodium thiosulfate pentahydrate was 2.9 mg, and chloroauric acid was 2.8 mg. The average projected area diameter for all particles with an aspect ratio of 3 or more is 1.1μ.
m, the standard deviation was 15%, and the aspect ratio was 7.0.

Preparation of coating liquid Emulsion layer coating liquid-Emulsion-A and -C were mixed in a ratio of 1/1 (equal amount) to prepare a coating liquid by adding the following chemicals to 1 mol of silver halide. -Adjusted amount to be gelatin Ag / gelatin 0.8-Polymer latex [poly (ethyl acrylate / methacrylic acid) = 97/3] 25.0 g- 1,2-bis (sulfonylacetamide) ethane 8 mmol / surface Per 100 g of gelatin in the protective layer and emulsion layer 12 g of potassium hydroquinone monosulfonate 2 80 g of 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 80 g of sodium polyacrylate (average molecular weight) 41,000) -Potassium polystyrene sulfonate 1.0 g (average molecular weight 600,000)

Emulsion layer coating solution-Emulsion layer coating solution-A coating solution was prepared in exactly the same manner as coating solution-except that the amount of gelatin added was adjusted to Ag / gelatin = 1.0.

Emulsion Layer Coating Solution-A coating solution-was prepared in exactly the same manner as the coating solution-except that the emulsion was emulsion-B and the amount of gelatin added was adjusted so that Ag / gelatin was 1.3.

Emulsion Layer Coating Solution-A coating solution was prepared in exactly the same manner as the coating solution except that the emulsion was emulsion B and the amount of gelatin was adjusted so that Ag / gelatin was 1.0.

[Support] Biaxially stretched thickness 175 μm
Corona discharge treatment was performed on the blue-dyed polyethylene terephthalate film, and both sides were coated with a wire bar coater so that the coating amount per one side became the following coating amount, followed by drying at 185 ° C. for 1 minute. Subbing lower layer Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio ^{/ 31/69 0.322g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 8.4 mg / m ²

[0021]

[Chemical 2]

Undercoat upper layer ・ Gelatin 300 mg / m ²・ Polyethylene acrylate 20 mg / m ²・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 4 mg / m ²

[0023]

[Chemical 3]

The dye used here has a magenta color, and the dispersion in the microcrystalline state (0.2 μm) was added to the gelatin solution by the following preparation method. 20 g of the dye, 200 g of a 1% aqueous solution of carboxymethyl cellulose and 287 g of H ₂ O were mixed, and the mixture was treated for 8 hours at 5000 rpm in an Eiger mill (Eiger Japan KK) using beads of zirconium oxide (ZrO ₂ ) having a diameter of 2 mm.

Preparation of Photosensitive Materials I and II A polyethylene terephthalate support doped with the above-mentioned blue dye containing a magenta dye in the undercoat upper layer was prepared according to the above-mentioned emulsion layer coating solutions --- and surface protective layer solutions. Was coated on both sides of the support to prepare Photosensitive materials I and II. (Table I)

[0026]

[Table 1]

The surface protective layer is the same on both the A side and the B side.
The composition and coating amount are described below.

Contents of the surface protective layer: Gelatin 1.15 g / m ² Polyacrylamide 0.25 g / m ² (average molecular weight 45,000) Sodium polyacrylate 0.02 g / m ² (average molecular weight 400,000) · p-t-octylphenoxy sodium salt, poly (polymerization degree 10) diglyceryl 0.02 g / m ² butyl sulfone compound oxyethylene - poly (polymerization degree 3) 0.01 g / m ² Okishiguriseriru -p- octylphenoxy Ether ・ C ₈ F ₁₇ SO ₃ K 0.003 g / m ²

[0029]

[Chemical 4]

Polymethyl methacrylate 0.025 g / m ² (average particle size 3.5 μm) Poly (methyl methacrylate / methacrylate) 0.020 g / m ² (molar ratio 7: 3, average particle size 2.5 μm)

Evaluation of Scratch Resistance After sensitizing the photosensitive materials-1 and -2 under conditions of 25 ° C and 25% RH for 1 hour, a commercially available nylon scrubbing tool was used under the same conditions and a weight of 80 g was applied to an area of 2 x 1 cm. And rubbed at a speed of 1 cm per second. In the unexposed state, an automatic developing machine CEPROS-M manufactured by Fuji Photo Film Co., Ltd., and CE-D-F1 as a developing solution and a fixing solution were used for development at 35 ° C. and fixing at 32 ° C. for 45 seconds (Dry to Dry). After that, the number of blackened score marks was counted. Light-sensitive material of the present invention-I
The number of scratches (18) was less than 1/2 of the number of scratches (44) of Comparative Sample Photosensitive Material-II.

Evaluation of Photographic Performance SA / SA ', S determined according to the method described in the specification.
A / SB and γB / γA are as shown in Table II below.

[0033]

[Table 2]

From the evaluation of scratch resistance and the evaluation of photographic performance, it is understood that the photographic material-I of the present invention satisfies the desirable photographic performance conditions for satisfying the sharpness and the graininess, and has less scratch blackening.

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[Procedure amendment]

[Submission date] July 29, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

Preparation of coating liquid Emulsion layer coating liquid-Emulsion-A and -C were mixed in a ratio of 1/1 (equal amount) to prepare a coating liquid by adding the following chemicals to 1 mol of silver halide. -Adjusted amount so as to be gelatin Ag / gelatin 0.8-Polymer latex [poly (ethyl acrylate / methacrylic acid) = 97/3] 25.0 g- 1,2-bis (vinylsulfonylacetamide) ethane 8 mmol / Per 100 g of gelatin in the surface protective layer and emulsion layer: 12 g of potassium hydroquinone monosulfonate, 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 80 mg, sodium polyacrylate, 4.0 g (average) Molecular weight 41,000) -Potassium polystyrene sulfonate 1.0g (average molecular weight 600,000)

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

[0029]

[Chemical 4]

Claims (1)

[Claims] 1. Both sides of a support (referred to as A side and B side, respectively)
In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer, the sensitivity of the A side when exposed only from the A side is SA and the gradation is When the γA and B surface sensitivities are SB ′, the B surface sensitivity when exposed from the B surface side is SB, the gradation is γB, and the A surface sensitivity is SA ′, SA and SB,
SA ′, SB ′ γA, γB are represented by the following formulas [I], [II],
[I] SA / SA ′> 4.0 [II] SA / SB = 0.8 to 1.5 [III] γB / γA> 1.1 and A silver halide photographic light-sensitive material characterized in that the silver (A) / gelatin (A) (weight) ratio of the emulsion layer is smaller than the silver (B) / gelatin (B) (weight) ratio of the emulsion layer on the B side. ..