JPH0756254A - Silver halide photographic sensitive material and radiation image forming method using the same - Google Patents

Abstract

PURPOSE:To provide a silver halide photosensitive material which ameliorates unequal drying in ultra-rapid processing and has an excellent diagnostic capacity. CONSTITUTION:This silver halide photographic sensitive material is a photographic sensitive material having at least one layer of silver halide photosensitive emulsion layers on both sides of a transparent base, also, is a photographic sensitive material constituting a radiation image forming assembly consisting of two sheets of radiation intensifying screens arranged on the front side and rear side, respectively, of this photographic sensitive material, and has such a sensitivity that the exposure necessary for the concentration obtd. in the photosensitive layer attains the value obtd. by adding 0.5 to the min. concentration is 0.011 to 0.045 lux second when the photosensitive material is exposed by monochromatic having the same wavelength as the main light emission peak wavelength of the radiation screens and 20+ or -5nm half-width, is subjected to development processing for 25 second developing time at 35 deg.C developing temp. by using a developer and is measured after peeling the photosensitive layer on the side reverse to the exposed surface. The melting time of the photosensitive material described above is >=8 to <80 minutes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel silver halide photographic light-sensitive material and a novel X-ray image forming method. The present invention relates to a silver halide photographic light-sensitive material and an image forming method thereof, which improves drying unevenness occurring in a processing and drying step and provides an excellent image.

[0002]

2. Description of the Related Art In medical radiography, an image of a patient's tissue is obtained by using a photographic light-sensitive material (silver halide photographic light-sensitive material) containing at least one light-sensitive silver halide emulsion layer coated on a transparent support. It is used by recording an X-ray transmission pattern on the silver halide photographic light-sensitive material. The X-ray transmission pattern can be recorded by using the silver halide photographic light-sensitive material alone. However, since it is not desirable for the human body to be exposed to a large amount of X-ray exposure, X-ray photography is usually carried out by combining a radiation intensifying screen with a silver halide photographic light-sensitive material. The radiographic intensifying screen is provided with a phosphor layer on the surface of a support, and the phosphor layer absorbs X-rays,
In order to convert visible light, which has high photosensitivity for photosensitive materials,
Its use can significantly improve the sensitivity of the X-ray imaging system.

As a method for further improving the sensitivity of an X-ray photography system, a light-sensitive material having photographic emulsion layers on both sides, that is, a silver halide photographic having silver halide photographic light-sensitive layers on the front side and the back side of a support, respectively. A method has been developed in which a photosensitive material is used, and both sides of it are sandwiched by a radiation intensifying screen (sometimes referred to simply as an intensifying screen). Various shooting methods are used. This method is a method developed because a sufficient amount of X-ray absorption cannot be achieved by using a single intensifying screen. That is, even if the phosphor amount of one intensifying screen is increased to increase the X-ray absorption amount, the visible light converted in the phosphor layer thickened due to the increase is scattered inside the phosphor layer. Since the light is reflected, the visible light emitted from the intensifying screen and incident on the photosensitive material arranged in contact with the intensifying screen is greatly blurred. Further, since visible light generated in the deep part of the phosphor layer is difficult to be emitted from the phosphor layer, even if the phosphor layer is unnecessarily increased, effective visible light emitted from the intensifying screen is not sensitized. Therefore, the X-ray imaging method using two intensifying screens having a phosphor layer of an appropriate thickness increases the X-ray absorption amount as a whole and the visible light effectively converted from the intensifying screen. Has the advantage that it can be taken out. Research to find an X-ray imaging system that is excellent in the balance between image quality and sensitivity has been continuously conducted until now. For example, conventionally, a combination of a blue emission intensifying screen having a phosphor layer of a calcium tungstate phosphor and a silver halide photographic light-sensitive material which has not been spectrally sensitized (eg, high screen standard and RX (both Fuji Photo Film Co., Ltd. product name)
Was used commonly, but recently,
A combination of a green emission intensifying screen having a phosphor layer of a terbium-activated rare earth element oxysulfide phosphor and an ortho-spectral-sensitized silver halide photographic light-sensitive material (eg, Grinex 4 and RXO (both Fuji Photo Film) (Commercial name) (trade name) is used, and improved results have been obtained in both sensitivity and image quality.

On the other hand, a combination of a silver halide photographic light-sensitive material having photographic emulsion layers on both sides and a radiation intensifying screen is set under specific conditions to find an X-ray photographing system excellent in the balance of image quality and sensitivity. Attempts have also been made to get out. For example, JP-A-2-266344 and 2-
297544 and U.S. Pat. No. 4,803,150 have opposite optical characteristics (sensitivity) obtained by combining an intensifying screen (front intensifying screen) on the X-ray irradiation side with a photosensitive layer (front photosensitive layer). The light characteristics (sensitivity) obtained by the combination of the side intensifying screen (rear surface intensifying screen) and the photosensitive layer (rear surface photosensitive layer) are set to be different from each other, and the former combination and the latter combination are An X-ray imaging system that is set so as to show mutually different contrasts is disclosed. On the other hand, on page 40 of Photographic Science and Engineering, Vol. 26, No. 1 (1982), in the combination of a radiation intensifying screen manufactured by 3M and a silver halide photographic light sensitive material, Trimax 12 (3M) (Commercial name of commercial intensifying screen) and XUD (commercial name of commercial silver halide photographic material of 3M) are combined with Trimax4 (commercial name of commercial intensifying screen of 3M) and XD (commercial intensifying screen of 3M). About the same sensitivity and sharpness (MTF) as the combination with commercial silver halide photographic material)
, But shows the experimental result that a high NEQ (output signal to noise ratio) is given. And, this result teaches that XUD shows a higher sharpness than XD, while Trimax12 shows a higher X-ray absorption amount than Trimax4.

Of course, if attention is paid only to the image quality of the X-ray image,
It was possible to obtain a high-quality X-ray image by using a low sensitivity silver halide photographic light-sensitive material in combination with a similarly low-sensitivity radiation intensifying screen. However, when such a combination of low sensitivities is used, the exposure dose (exposure dose) of X-rays to the human body is inevitably increased. When most of the subjects are healthy people, it is necessary to avoid increasing the dose as much as possible.
You can't actually use it.

Further, in recent years, rapid processing for processing dry to dry in 90 seconds or less has become widespread. In order to enable rapid processing, strengthening the drying capacity of the automatic processor is an important issue.
However, accompanying the strengthening of the drying ability, unevenness in drying due to nonuniform drying is likely to occur in the processed light-sensitive material.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic material and an image forming method for the same, which can improve the drying unevenness particularly in rapid processing and provide an image having excellent diagnostic ability. To aim.

[0008]

Means for Solving the Problems As a result of intensive studies by the present inventor, a photographic light-sensitive material having at least one silver halide light-sensitive emulsion layer on both sides of a transparent support, the front side of the photographic light-sensitive material and A photographic light-sensitive material constituting a radiation image forming assembly composed of two radiation intensifying screens arranged on the rear side, each having a wavelength equal to the main emission peak wavelength of the radiation screen and having a half width of 20. ±
The photosensitive layer was exposed to a monochromatic light of 5 nm, developed using the developing solution [I] at a developing solution temperature of 35 ° C. and a developing time of 25 seconds, and the photosensitive layer on the side opposite to the exposed surface was peeled off and measured. The exposure amount required for the density obtained in step 1 to be a value obtained by adding 0.5 to the minimum density is 0.011 lux seconds to 0.045 lux seconds, and the melting time is 8 8 minutes or more
The object of the present invention has been achieved by a silver halide photographic light-sensitive material characterized by being less than 0 minutes. Developer [I] Potassium hydroxide 21 g Potassium sulfite 63 g Boric acid 10 g Hydroquinone 25 g Triethylene glycol 20 g 5-Nitroindazole 0.2 g Glacial acetic acid 10 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Methylbenzotriazole 0.05 g Glutar Aldehyde 5g Potassium bromide 4g Add water to make 1 liter and adjust to pH 10.10.

The standard conditions of the developing process using the developing solution [I] will be described in more detail below. Development time: 25 seconds (21 seconds in liquid + 4 seconds outside liquid) Fixing time: 20 seconds (16 seconds in liquid + 4 seconds outside liquid, fixing solution has the following composition) Water washing: 12 seconds Squeeze and dry: 26 Second developing device: Commercial roller-conveying automatic developing machine (eg,
Fuji Photo Film Co., Ltd. FPM-5000 automatic developing machine) (Developing tank: capacity 22 liters, liquid crystal 35 ° C.) (Fixing tank: capacity 15.5 liters, liquid crystal 25 ° C.) Eastman Kodak M-6AW is available. Fixer (Fixer F) composition Ammonium thiosulfate (70% weight / volume) 200 ml Sodium sulfite 20 g Boric acid 8 g Ethylenediaminetetraacetic acid disodium salt (dihydrate) 0.1 g Aluminum sulfate 15 g Sulfuric acid 2 g Glacial acetic acid 22 g Water was added 1 After adjusting to liter, pH is adjusted to 4.5 with sodium hydroxide or glacial acetic acid as needed.

The melting time must be 8 minutes or more and less than 80 minutes, preferably 12 minutes or more and 60 minutes or less. If it is less than 8 minutes, gloss unevenness (referred to as drying unevenness) due to uneven drying tends to occur. on the other hand,
When it is 80 minutes or more, the residual color of the sensitizing dye increases. Here, the melting time is measured by immersing a silver halide photographic light-sensitive material cut into 1 cm × 2 cm at 50 ° C. in an aqueous solution of 1.5% by weight of sodium hydroxide to form at least one layer of the silver halide photographic light-sensitive material. Say the time it takes to start melting.

In order to obtain a preferable melting time in the present invention, a known gelatin hardening agent is used. This can be achieved by devising the addition amount, the drying method and the like.
At least one layer of the silver halide photographic light-sensitive material of the present invention cured with at least one type of hardener selected from vinyl sulfone type hardeners and halogen-substituted-S-triazine type hardeners. preferable. Having a hydrophilic colloid layer containing at least one photosensitive silver halide emulsion layer on a support means that at least one photosensitive silver halide emulsion layer is formed on at least one surface of the support, and According to the above, a non-photosensitive hydrophilic colloid layer, for example, a packing layer, an intermediate layer, a protective layer or the like is provided on the support. A preferred vinyl sulfone-based hardener used in the present invention is, for example, German Patent No. 1,10.
Aromatic compounds as described in JP-A-0,942, JP-B-44-92222 and alkyl compounds bonded with a hetero atom as described in JP-B-47-25373 and JP-B-47-8736. Sulfonamides, ester compounds as described, JP-A-49-2443
1,3,5-tris [β- as described in No. 5
(Vinylsulfonyl) -propionyl] -hexahydro-s-triazine or alkyl compounds such as those described in JP-A-51-44164 are included. Typical specific examples thereof are shown below (H-1) to (H-22), but the present invention is not limited thereto.

[0012]

[Chemical 1]

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

The vinyl sulfone type hardener which can be used in the present invention is, in addition to the above exemplified compounds, a compound having at least 3 vinyl sulfone groups in the molecular structure, for example, exemplified compounds (M-5) to (H). -22), a compound having a group reactive with a vinyl sulfone group and a water-soluble group,
For example, it includes a reaction product obtained by reacting diethanolamine, thioglycolic acid, sarcosine sodium salt, and taurine sodium salt.

Next, the halogen-substituted-s-triazine type hardener is preferably a compound represented by the following general formula [I] or [II]. General formula [I]

[0020]

[Chemical 7]

(In the above general formula [I], R ₁ is chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -OM group (M is a monovalent metal atom), -NR ¹ R
² groups (provided that R ¹ and R ² are a hydrogen atom, an alkyl group, and an aryl group respectively) or —NHCOR ³ group (R ³ is a hydrogen atom, an alkyl group, an aryl group), and R ₂ excludes a chlorine atom. Represents a group having the same meaning as R ₁ above). General formula (I
I]

[0022]

[Chemical 8]

(In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or-
It represents an OM group (M is a monovalent metal atom). Q and Q ′ are respectively a linking group selected from —O—, —S—, and —NH—,
L represents an alkylene group or an arylene group. l and m
Each represent 0 or 1. ) Specific examples of the compound represented by the above general formula [I] or [II] are shown below, but the present invention is not limited thereto.

[0024]

[Chemical 9]

These hardeners are added in an amount of 0.5 to 100 mg, preferably 2.0 to 50 mg, per 1 g of coated gelatin.

The photographic emulsion used in the present invention is P. Glafkide.
s Chimie et Physique Photographique (Paul Monte
Published by GF Duffin, Photographic Em
ulsion Chemistry (The Focal Press, 1966
,) By VL Zelikman et al Making and Coting Photo
graphic Emulsion (The Focal Press, 1964
), JP-A-58-127921 and 58-113.
It can be adjusted using the method described in Japanese Patent Publication No. 926. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, a one-sided mixing method, a simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method of forming silver halide grains in the presence of excess silver ions (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion comprising silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. Even if the crystal structure of the silver halide grains is uniform even in the inside, it has a layered structure in which the inside and the outside are different, and British Patent 635,841 and British Patent 3,62.
It may be a so-called conversion type as described in No. 2,318. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver rhodanide and silver oxide, for example. Further, it may be either a surface latent image type or an internal latent image type. Coexist with cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt in the process of silver halide grain formation or physical ripening during the production of silver halide. You may let me. In addition, at the time of particle formation, ammonia, thioether compound, thiazoline-
2-Thion, tetra-substituted thioureas may be used.

The tabular silver halide emulsion is a knuck (Cu
Gnac) and Chateau (Advance of the Morphology of Silver Bromide during Silver Physical Evolution (Silver Bromide of Silver Promide Crystals Dualing Physical Raising)) Science E-Industrie Photography, 33
Vol. No. 2 (1962), p. 121-125, Duffin, "Photographic emulsion chemistry," Focal Press, New York, 196.
6 years, p. 66-p. 72, APH Trivel (Trivell
i), WF Smith Photographic Journal, 80, 285 (19
40) and the like, but JP-A-58-127,9
21, JP-A-58-113,927, JP-A-58-
It can be easily adjusted by referring to the methods described in 113,928 and British Patent No. 4,439,520. Further, a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere having a relatively low pBr value of pBr1.3 or less is formed,
It can be obtained by growing a seed crystal while simultaneously adding silver and a halogen solution while maintaining the same pBr value. During this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. The size of tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of solvent, and controlling the addition rate of silver salt and halide used during grain growth.

The chemical sensitization of the silver halide emulsion is preferably carried out using at least one of noble metal sensitization, sulfur sensitization and reduction sensitization. Chemical sensitization is described by TH James, The Theory of the Photographic Process, 4th Edition, McClamine, 1977, p. 67-76 with active gelatin, and Research Disclosure, Vol. 120, Apr. 1974, Item 12008, Research Disclosure, 1.
34, June 1975, Item 13452, U.S. Pat. Nos. 1,623,499 and 1,673,522.
No. 2,399,083, 2,642,36
No. 1, No. 3,297,447, No. 3,297,4
No. 46, No. 3,772,031, No. 3,761,
No. 267, No. 3,857,711, No. 3,56
5,633, 3,901,714 and 3,904,415 and British Patent 1,315,7.
55 and 1,396,696, pAg 5-10, pH 5-8 and temperature 30-80.
It can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, and combinations of these sensitizers at ° C. Chemical sensitization is most suitable in US Pat.
42,361, and in the presence of thiocyanate compounds, and US Pat. No. 2,521,926,
No. 3,021,251 and No. 4,054,45
It is carried out in the presence of a sulfur-containing compound of the type described in No. 7. It can also be chemically sensitized in the presence of a finish (chemical sensitization) modifier. Finishing modifiers used include azaindene, azapyridazine, azapyrimidine,
Benzthiazolium salts and compounds known to suppress fog and increase sensitivity in the process of chemical sensitization, such as sensitizers having one or two or more heterocyclic nuclei are used. . Examples of finish modification examples are US Pat.
No. 31,038, No. 3,411,914, No. 3,
544,757, 3,565,631 and 3,901,714, Canadian Patent 778,723.
Issue and Duffin, Photographic Emulsion Chemistry Focal Press (19
66), New York, pp. 138-143. Further, chemical sensitization in the presence of commonly used sensitizing dyes is also useful for obtaining an emulsion having high sensitivity and good development progress.

Further, as described in US Pat. Nos. 3,891,446 and 3,984,249, reduction sensitization can be performed by using, for example, hydrogen, and US Pat. No. 2,983. , 609, oftedar
l) et al., Research Disclosure, Vol. 136, 1
August 975, Item 13654, US Patent No. 2,5
No. 18,698, No. 2,739,060, No. 2,
743,182, 2,743,183, 3,026,203 and 3,361,564, such as stannous chloride, thiourea dioxide, polyamines and amineboranes. Using a reducing agent
Or low pAg (eg less than 5) and / or high pH
Reduction sensitization can be performed by treatment (for example, greater than 8).

There are no particular restrictions on the technique of other various additives used in the light-sensitive material of the present invention, and those described in the following relevant parts of JP-A-2-68539 can be used. Item This section 1 Antifoggant / Stabilizer JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to same Page 4, lower left column. 2 Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 3 Surfactant / antistatic, page 11, upper left column, line 14 to page 12, upper left column, agent 9 line. 4 Matting agents, slip agents, yes Yes, page 12, upper left column, line 10 to same upper right column, line 10 Plasticizer. Page 14, lower left column, line 10 to lower right column, line 1 of the same. 5 Hydrophilic colloid, page 12, upper right column, line 11 to lower left column, line 16 6 Supports, page 13, upper right column, lines 7 to 20. 7 Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9

The silver halide photographic light-sensitive material of the present invention is a commercially available high-sensitivity screen, for example, HR-6, HR-8, HR-12, HR-12, etc. available from Fuji Photo Film (KK).
Can be used in combination with. Furthermore, Japanese Patent Application No. 5
A radiation intensifying screen having a high X-ray absorptivity and an excellent sharpness, which is described in claim 4 of No. 121675, can be preferably used.

[0032]

【Example】

Example 1 Preparation of Tabular Emulsion A Potassium bromide 6.9 g, average molecular weight 1 in 1 liter of water.
5,000 g of low-molecular weight gelatin 5,000 g was added, and while stirring in a container kept at 55 ° C., 37 cc of an aqueous solution of silver nitrate (2.4 g of silver nitrate) and an aqueous solution containing 5.9 g of potassium bromide 38
cc was added by the double jet method in 37 seconds. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 100 cc of silver nitrate aqueous solution (silver nitrate 11.2 g) was added over 22 minutes. Here, 8.5 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 8 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 145 g of silver nitrate and an aqueous solution of potassium bromide were added to pAg.
Flow rate accelerated by the control double jet method while maintaining 8.5 (initial flow rate / final flow rate = 1 / 5.4) 35
Added over minutes. Then, 35 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Average projected area diameter 1.
Pure silver bromide tabular grains having a diameter of 25 .mu.m, a thickness of 0.18 .mu.m and a variation coefficient of 20% were obtained. After this, soluble salts were removed by the coagulation sedimentation method. The temperature was raised again to 40 ° C., 35 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 with caustic soda and silver nitrate solution, pAg.
Adjusted to 8.00. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, add C ₂ H ₅ SO ₂ SNa to 1
× 10 ^-5 mol / mol Ag was added, then 0.1 mol% of AgI fine particles was added, and then 480 mg of Sensitizing Dye-I was added.
Was added. Further, 0.83 g of calcium chloride was added. Subsequently, 0.9 mg of sodium thiosulfate, 1.9 mg of selenium compound-I, 1.9 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. Thus, preparation of tabular grain emulsion A was completed.

[0033]

[Chemical 10]

Preparation of Fine Particle Emulsion B Into 1 liter of a 2% by weight gelatin solution containing 5.3 g of potassium bromide and 4 g of sodium paratoluenesulfinate, 10 mg of sodium thiosulfate pentahydrate, 4.0 g of rhodanic potassium, Glacial acetic acid (10 cc) was added, and the mixture was vigorously stirred by the double jet method in an amount of 14 cc of an aqueous solution containing 5.2 g of silver nitrate, 1.8 g of potassium bromide and 0.1 g.
7 cc of an aqueous solution containing 33 g of potassium iodide was added over 30 seconds. Then, 30 cc of an aqueous solution containing 3 g of potassium iodide was added thereafter. First, 200 cc of an aqueous solution containing 78 g of silver nitrate was added to the above solution, and after 1 minute, 5 cc.
200 cc of an aqueous solution containing 0.6 g of potassium bromide and 3.65 g of potassium iodide was added over 15 minutes. Next, after adding 14 cc of 25 wt% ammonia water and aging for 10 minutes, an aqueous solution containing 117 g of silver nitrate and an aqueous solution containing 82.3 g of potassium bromide were simultaneously added to 1
Added in 4 minutes. The temperature of the reaction solution in all steps was maintained at 70 ° C. The above reaction liquid was washed by a flocculation method by a conventional method, and gelatin was added at 40 ° C.
After adding and dispersing a thickener and a preservative, the pH was adjusted to 5.6 and the pAg was adjusted to 8.9. Next, this reaction solution is added to 55
4-hydroxy-6-methyl-1, while maintaining at ℃,
21 mg of 3,3a, 7-tetrazaindene and sensitizing dye I
460 mg was added and the mixture was aged for 10 minutes, then sodium thiosulfate pentahydrate 3.8 mg and selenium compound II 3.8 were added.
mg, Rhodankari 77 mg, and chloroauric acid 2.6 mg were added successively, aged for 50 minutes, and then 4-hydroxy-6.
-Methyl-1,3,3a, 7-tetrazaindene 70 mg
Was added and then cooled to obtain a fine particle monodisperse non-tabular grain emulsion B. The average equivalent spherical diameter was 0.68 μm, and the variation coefficient of particle size was 20%.

[0035]

[Chemical 11]

Preparation of Support Corona discharge treatment was performed on a biaxially stretched blue-colored polyethylene terephthalate film having a thickness of 175 μm, and the first undercoat liquid having the following composition was applied at an amount of 4.
It was coated with a wire bar coater so as to be 9 cc / m ² and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface.・ Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158cc ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41cc ・ Distilled water 300cc Above A second undercoat layer having the following composition on each side of the first undercoat layer on both sides, so that the coating amount is one on each side and the wire bar coater method is applied to both sides at 155 ° C.
It was applied and dried.・ Gelatin 160 mg / m ²・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 1.8 mg / m ²・ Proxel 0.27 mg / m ²・ Mat agent Polymethylmethacrylate having an average particle size of 2.5 μm 2. 5 mg / m ²

Preparation of Coating Solution The following chemicals were added to Emulsion A to prepare a coating solution for emulsion layer. Further, a protective layer coating solution was prepared. (Emulsion coating solution) -Emulsion A 1 kg (gelatin 62 g, Ag: 94 g) -Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3, weight ratio) 24.4 g-Hardener (1,2- Bis (vinylsulfonylacetamide) ethane) Add an amount that gives a melting time of 35 minutes. 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 0.13 g. Sodium polystyrene sulfonate ( Average molecular weight 600,000) 5.3g Dextran (average molecular weight 39,000) 28g Gelatin gel (as solid content) 61g

[0038]

[Chemical 12]

(Protective layer coating liquid) -Gelatin 1 kg-Dextran (average molecular weight 39,000) 200 g-C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₁₀ H 39 g-C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) SO ₃ Na 1.6 g ・ C ₈ F ₁₇ SO ₃ K 7 g ・ Polymethylmethacrylate particles (average particle diameter 3.7 μm) 91 g ・ Proxel 0.7 g ・Sodium polyacrylate (average molecular weight 41,000) 45 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 3 g ・ NaOH 1.6 g ・ C ₈ H ₁₇ C ₆ H ₄ (OCH ₂ CH ₂ ) ₃ SO ₃ Na 24 g・ Distilled water upto 14.4 liters

The coating liquid prepared in the preparation of the light-sensitive material was applied simultaneously on both sides of the support prepared in the same condition by the simultaneous extrusion method. The amount of gelatin in the protective layer was 1 g / m ² . Photosensitive Material-X was prepared with the amount of coated silver being 1.8 g / m ² per side. Next, a light-sensitive material-Y was prepared in the same manner as the light-sensitive material-X except that the emulsion B was used instead of the emulsion A and the coated silver amount was 1.6 g / m ² per side.

Measurement of Absolute Sensitivity of Photosensitive Material The absolute sensitivity of the prepared sample and a commercially available photosensitive material Super HRS (manufactured by Fuji Photo Film) was examined. Transmission peak wavelength 545nm
A tungsten light source with a color temperature of 2856 K ° (a light of 545 nm depending on the filter--corresponding to the main emission wavelength of the radiographic intensifying screen to be used together later--) is used as a central light source by using a filter having a half-width of 20 nm and a transmittance of 20 nm. The photographic light-sensitive material was exposed by using (selected and used) as irradiation light, and its sensitivity was measured. That is, the above irradiation light was passed through a neutral step wedge to irradiate the photosensitive material for 1/20 seconds to perform exposure. After the exposure, the photosensitive material was changed to an automatic developing machine (Fuji Photo Film Co., Ltd., trade name FPM-500).
In (0), the developing solution (I) was used for development at 35 ° C. for 25 seconds (total processing time 90 seconds). After peeling off the photosensitive layer on the side opposite to the exposed surface, the density was measured, a characteristic curve was obtained, and the exposure amount required to obtain a density obtained by adding 0.5 to the minimum density (Dmin) was calculated from the characteristic curve. The sensitivity is shown in Table 8 in lux seconds. In calculating the exposure amount, the illuminance of the light emitted from the tungsten light source and transmitted through the filter was measured with a PI-3F type illuminometer (rehabilitated).

[0042]

[Table 1]

Image evaluation by chest phantom Chest phantom manufactured by Kyoto Kagaku Co., Ltd., three-phase 12-pulse 1
00KVp (3mm thick aluminum equivalent filter device), X-ray source with focal spot size 0.6mm × 0.6mm, placed phantom at 140cm distance, and then cut scatter ray with grid ratio 8: 1. Photographing was performed by placing a grid and then an assembly of a light-sensitive material and an intensifying screen. The assembly is a commercially available HR-3 screen / photosensitive material-X (comparative) manufactured by Fujifilm and a HR-8 screen / photosensitive material-Y manufactured by Fujifilm.
(Present invention). Dry-to-dry 45 seconds processing was carried out using an automatic processor CEPROS-M / processing agent CE-D-FI (manufactured by Fuji Photo Film Co., Ltd.) at development 35 ° C. and fixing 32 ° C. The granularity of the chest phantom practice of the assembly was far superior to that of the assembly.

Example 2 A light-sensitive material-Z (comparative) was prepared in exactly the same manner as the light-sensitive material-Y except that the amount of hardener was adjusted so that the melting time of the light-sensitive material was 7 minutes. The same chest phantom technique as in Example 1 was performed in combination with the HR-8 screen to perform the CEPROS-M treatment. When the drying unevenness was examined, periodic unevenness of gloss was recognized in parallel with the film conveying direction in the automatic developing machine. Photosensitive material of Example 1-Y
In the case of dryness, almost no uneven gloss was observed.

Example 3 Preparation of Intensifying Screen As a coating liquid for forming a phosphor sheet, phosphor (Gd ₂ O ₂
S: Tb) 200 g, Binder A (Polyurethane, manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Desmolac TPK
L-5-2625 [solid content 40%]) 20 g, and binder B (nitrocellulose, nitrification degree 11.5%) 2 g
Was added to a methyl ethyl ketone solvent and dispersed by a propeller mixer to prepare a coating liquid having a viscosity of 30 PS (25 ° C.) (binder / phosphor ratio = 1/20). This was applied onto polyethylene terephthalate (temporary support, thickness: 180 μm) coated with a silicone-based release agent to give a film thickness of 160
It was applied so as to have a thickness of μm (film thickness after pressure compression treatment described later), dried, and then peeled from the temporary support pair to form a phosphor sheet. Separately, as an undercoat layer forming coating solution, 90 g of a hard acrylic resin and 50 g of nitrocellulose were added to methyl ethyl ketone and mixed and dispersed to have a viscosity of 3 to 6 PS (2
A dispersion liquid (5 ° C) was prepared.

250 μm thick with titanium dioxide kneaded
Polyethylene terephthalate (support) is placed horizontally on a glass plate, the above coating solution for forming the undercoat layer is uniformly applied on the support using a doctor blade, and then the temperature is gradually raised from 25 ° C to 100 ° C. And the coating film was dried to form an undercoat layer on the support (coating film thickness:
15 μm). The phosphor sheet prepared first was placed on this, and pressure compression operation was performed using a calender roll at a pressure of 400 Kgw / cm ² and a temperature of 80 ° C.

Separately, fluororesin (fluorofine
Vinyl ether copolymer, Asahi Glass Co., Ltd., trade name: Lumiflon LF100) 70 g, cross-linking agent (isocyanate, Sumitomo Bayer Urethane Co., Ltd., trade name: Desmodur Z4370) 25 g, bisphenol A type epoxy resin 5 g, and alcohol Modified silicone oligomer (having dimethylpolysiloxane skeleton and having hydroxyl groups (carbinol groups) at both ends, Shin-Etsu Chemical Co., Ltd.)
Product name: X-22-2809 (5 g), product name, was added to a mixed solvent of toluene / isopropyl alcohol (1: 1, volume ratio) to prepare a coating liquid for forming a protective film. The above coating solution for forming a protective film is applied to the surface of the phosphor sheet that has been subjected to a pressure compression operation on a support using a doctor blade,
It was heat-treated at 120 ° C. for 30 minutes, dried and thermoset to form a transparent protective film having a thickness of 3 μm. As described above, a radiation intensifying screen A composed of the support, the undercoat layer, the phosphor layer, and the transparent protective film was produced.

Measurement of characteristics of radiation intensifying screen 1) Measurement of X-ray absorption amount X-rays generated from a tungsten target tube operated at 80 KVp with three-phase power supply are transmitted through an aluminum plate having a thickness of 3 mm. , The sample radiation intensifying screen fixed at a position 200 cm from the tungsten anode of the target tube, and then the amount of X-rays transmitted through the intensifying screen at a position 50 cm after the phosphor layer of the intensifying screen. The amount of X-ray absorption was determined by measurement using an ionization type dosimeter. In addition, as a reference, the X-ray dose at the above measurement position was measured without passing through the intensifying screen. X
The linear absorption was 32.5%, which was the same as that of HR-8 (rear side).

2) Measurement of modulation transfer function (CTF) An MRE single-sided photosensitive material manufactured by Eastman Kodak Co. was placed in contact with an intensifying screen to be measured, and a rectangular chart for MTF measurement (made of molybdenum, thickness: 80 μm). , Spatial frequency: 0 lines / mm to 10 lines / mm) were photographed. The chart was placed at a position 2 m from the X-ray tube, and the light-sensitive material and then an intensifying screen were placed in front of the X-ray source. Japanese Patent Application No. 5 for X-ray source, development processing conditions, and CTF measurement conditions
It is the same as Example 1 of No. 121675. CTF (1
(Screen / mm), screen A is 0.87, HR-8 (rear side)
Is 0.76; CTF (3 lines / mm) and screen A is 0.
49, HR-8 (rear side) was 0.34.

Image evaluation by chest phantom Using the photosensitive material-Y prepared in Example 1 (a) photosensitive material-Y / screen HR-8 (b) photosensitive material-Y / screen A (front side and rear side of photosensitive material) The chest phantom technique was performed in the same manner as in Example 1 by using the screen A on both sides. A sharper chest phantom image was obtained for the assembly (b) than for the assembly (a). The granules of the assembly (b) are the assembly
It was the same as (a).

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[Procedure amendment]

[Submission date] December 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

Of course, if attention is paid only to the image quality of the X-ray image,
It was possible to obtain a high-quality X-ray image by using a low sensitivity silver halide photographic light-sensitive material in combination with a similarly low-sensitivity radiation intensifying screen. However, when such a combination of low sensitivities is used, the exposure amount (exposure dose) of X-rays to the human body is inevitably increased, and such a combination is not preferable in practical use, and especially in mass screening. When most of the subjects are healthy people, it is necessary to avoid increasing the dose as much as possible.
You can't actually use it.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

The vinyl sulfone type hardener which can be used in the present invention is, in addition to the above exemplified compounds, a compound having at least 3 vinyl sulfone groups in the molecular structure, such as exemplified compounds (H-5) to (H. -22), a compound having a group reactive with a vinyl sulfone group and a water-soluble group,
For example, it includes a reaction product obtained by reacting diethanolamine, thioglycolic acid, sarcosine sodium salt, and taurine sodium salt.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Measurement of Absolute Sensitivity of Photosensitive Material The absolute sensitivity of the prepared sample and a commercially available photosensitive material Super HRS (manufactured by Fuji Photo Film) was examined. Transmission peak wavelength 545nm
A tungsten light source with a color temperature of 2856 K ° (a light of 545 nm depending on the filter--corresponding to the main emission wavelength of the radiographic intensifying screen to be used together later--) is used as a central light source by using a filter having a half width of 20 nm and a transmittance of 20 nm. The photographic light-sensitive material was exposed by using (selected and used) as irradiation light, and its sensitivity was measured. That is, the above irradiation light was passed through a neutral step wedge to irradiate the photosensitive material for 1/20 seconds to perform exposure. After the exposure, the photosensitive material was changed to an automatic developing machine (Fuji Photo Film Co., Ltd., trade name FPM-500).
In (0), the developing solution (I) was used for development at 35 ° C. for 25 seconds (total processing time 90 seconds). After peeling off the photosensitive layer on the side opposite to the exposed surface, the density was measured, a characteristic curve was obtained, and the exposure amount required to obtain a density obtained by adding 0.5 to the minimum density (Dmin) was calculated from the characteristic curve. The sensitivity is shown in Table 1 in lux seconds. In calculating the exposure amount, the illuminance of the light emitted from the tungsten light source and transmitted through the filter was measured with a PI-3F type illuminance meter (which has been rehabilitated).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

Measurement of characteristics of radiation intensifying screen 1) Measurement of X-ray absorption amount X-rays generated from a tungsten target tube operated at 80 KVp with three-phase power supply are transmitted through an aluminum plate having a thickness of 3 mm. The sample was fixed at a position 200 cm from the tungsten anode of the target tube to reach the radiographic intensifying screen, and the amount of X-rays transmitted through the intensifying screen was adjusted to 50 cm from the phosphor layer of the intensifying screen.
The amount of X-ray absorption was determined by measuring at a subsequent position using an ionization type dosimeter. In addition, as a reference, the X-ray dose at the above measurement position was measured without passing through the intensifying screen.
The X-ray absorption was 32.5%, which was the same as that of HR-8 (rear side).

Claims (3)

[Claims] 1. A photographic light-sensitive material having at least one silver halide light-sensitive emulsion layer on each side of a transparent support,
In a photographic light-sensitive material which constitutes a radiation image forming assembly composed of two radiation intensifying screens respectively arranged on the front side and the rear side of the photographic light-sensitive material, it has the same wavelength as the main emission peak wavelength of the radiation screen. And exposing with monochromatic light having a half width of 20 ± 5 nm and using the developing solution [I],
Development was carried out at a developing solution temperature of 35 ° C. and a development time of 25 seconds, the photosensitive layer on the side opposite to the exposed surface was peeled off, and then measured, and the density obtained in the photosensitive layer was 0.5 added to the minimum density. Exposure required to reach a value of 0.011 lux seconds to 0.045
Has a sensitivity of Lux seconds and a melting time of 8
Minutes or more and less than 80 minutes, a silver halide photographic light-sensitive material. Developer [I] Potassium hydroxide 21 g Potassium sulfite 63 g Boric acid 10 g Hydroquinone 25 g Triethylene glycol 20 g 5-Nitroindazole 0.2 g Glacial acetic acid 10 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Methylbenzotriazole 0.05 g Glutar Aldehyde 5g Potassium bromide 4g Add water to make 1 liter and adjust to pH 10.10. 2. At least one layer of a silver halide light-sensitive material comprises a vinyl sulfone type hardener and a halogen-substituted --S--.
The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is cured with at least one hardener selected from triazine-based hardeners. 3. A method of forming a radiographic image by sandwiching with the silver halide photosensitive material according to claim 1 and two radiographic intensifying screens having the following characteristics. (Radiation intensifying screen) At least one of the radiation intensifying screens exhibits an absorption amount of 25% or more for X-rays having an X-ray energy of 80 KVp and a contrast transfer function (CTF) of 1 spatial frequency / A radiographic intensifying screen with a mm of 0.79 or more and a spatial frequency of 3 / mm of 0.36 or more.