JPH117092A - Manufacture of silver halide photographic emulsion, silver halide photographic sensitive material, x-ray image forming method, and method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion low in fog and high in sensitivity and good in storage stability (fog and sensitivity) against time lapse and superior in processing aptitude in an ultrahigh-speed automatic developing machine by adding a specified amount of a thiocyanic acid compound to control pBr in a process from the time at which flat silver halide grains have grown to the start of a desalting process. SOLUTION: The silver halide grains contained in the silver halide emulsion contains the flat silver halide grains in >=50% of the total projection areas and having an aspect ratio of 3-15 and a corresponding circle diameter of >=0.5 μm. The aspect ratio means the corresponding circle diameter of the principal face to the thickness of the silver halide grain. The thiocyanic acid compound is added into the silver halide emulsion in the conditions of pBr of 2.5-3.5 in the process from the time of the flat silver halide grains having grown to >=90% of the completed flat grains to the start of the desalting process. The thiocyanic acid compound is added in an amount of 1×10<-2> -2×10<-1> mol per 1 mol of silver halide and then, bromide ions are added to convert pBr into 0.5-1.5, and after that, the desalting process is started.

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 (hereinafter, also simply referred to as "light-sensitive material"), a processing method thereof, a method for producing a silver halide photographic emulsion (hereinafter, silver halide emulsion), and an increase in fluorescence. The present invention relates to an X-ray image forming method for irradiating X-rays between paper sheets.

[0002]

2. Description of the Related Art One of the performances that are always required of photosensitive materials is to obtain a silver halide emulsion having higher sensitivity. For example, by increasing the sensitivity of X-ray sensitive materials,
The exposure dose of the subject can be reduced.

On the other hand, in recent years, the demand for rapid processing has increased, and the development of emulsions having excellent developability has been desired. Various techniques have been reported for the technique of increasing the sensitivity, but US Pat. Nos. 2,222,264 and 3,320,069.
And JP-A-62-18538 describe a method in which particles are formed in the presence of a thiocyanate to obtain particles having high sensitivity. However, in this technique, the addition amount of thiocyanate is several mol% with respect to silver, and the presence of such a large amount of thiocyanate in the silver halide emulsion has a disadvantage that storage stability is remarkably deteriorated. I have. US Patent No. 4,3
No. 32,887 discloses a technique in which thiocyanate is used as a silver halide solvent, but it is essential to remove the thiocyanate after grain formation, so that sufficient sensitivity can be obtained. Did not.

[0004] The amount of thiocyanate present on the grain surface must satisfy the condition of 2 × 10 ^-3 to 10 ^-2 mole per mole of silver. A general method is to use a desalting step after adding the thiocyanate. There is also a technique in which pBr is specified to be 2.5 or more in order to obtain a desired incorporation rate into silver halide grains. However, the deterioration of fog over time of the silver halide emulsions obtained by these known methods is still not at a satisfactory level, and the adsorption of the photosensitive dye is affected by the effect of the thiocyanate compound incorporated on the grain surface. Was extremely poor, and it became clear that desensitization over time occurred.

In order to solve these drawbacks, it is conceivable to reduce the amount of thiocyanate on the particle surface. However, as specified in the known literature, in the prior art, the thiocyanate uptake rate is low. Sufficient performance cannot be obtained.

The present inventors have found that the thiocyanate on the surface of the grains has a sensitizing effect even in a range lower than that of the conventional technique, and has a remarkably excellent storability over time, leading to the present invention.

[0007]

The present invention relates to a light-sensitive material, a processing method therefor, a method for producing a silver halide emulsion and a method for forming an X-ray image, and in particular, low fog, high sensitivity, storage stability with time (fog, sensitivity), Another object of the present invention is to provide a photosensitive material and an X-ray image forming method which are excellent in processability in an ultra-rapid automatic developing machine.

[0008]

SUMMARY OF THE INVENTION The above objects are as follows. At least 50% of the total projected area of the silver halide emulsion is tabular grains having an aspect ratio of 3 to 15, and the tabular grains grow from 90% or more of the finished grains to the start of the desalting step. Thiocyanate compound at 1 × 10 ^-2 to 2 × 10 per mol of silver under the conditions of pBr 2.5 to 3.5.
^A method for producing a silver halide photographic emulsion, wherein pBr is controlled to 0.5 to 1.5 after addition of ^-1 mol.

[0009] 2. 2. The method for producing a silver halide photographic emulsion according to claim 1, wherein silver iodide fine grains are added in a step from the point of 90% or more growth of the finished grains to the start of a desalting step.

[0010] 3. 3. The method for producing a silver halide photographic emulsion according to 1 or 2, wherein the pBr in the grain growth step up to 90% with respect to the finished grains is 1.0 to 2.5.

4. A silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support, characterized in that the emulsion layer contains the silver halide photographic emulsion described in 1 or 2 above. Silver halide photographic material.

5. The content of the thiocyanate compound present on the surface of the silver halide grains is 1 × 10 ^-4 per mol of silver.
5. The silver halide photographic material as described in 4, wherein the amount is 2 × 10 ^-3 mol.

The silver halide photographic material described in 6.4 or 5 is a silver halide photographic material having a photosensitive emulsion layer on both sides, wherein the silver halide photographic material has an X-ray energy of 80 kVp. X-rays irradiate X-rays between fluorescent intensifying screens having an absorption amount of 45% or more with respect to the line, a phosphor filling rate of 68% or more, and a phosphor thickness of 135 to 200 μm. An X-ray image forming method comprising performing exposure.

A method for processing a silver halide photographic light-sensitive material, characterized by processing the silver halide photographic light-sensitive material described in 7.4 or 5 in a processing step including a developing step and a fixing step.

[8] 8. The processing of the silver halide photographic light-sensitive material according to 7, wherein at least one of the development step and the fixing step supplies a solid processing agent and processes the silver halide photographic light-sensitive material while preparing a processing solution. Method.

9. 9. The processing method for a silver halide photographic light-sensitive material according to 8, wherein the processing is performed by a processing apparatus having a mechanism for supplying a solid processing agent to the processing layer.

10. Wherein the silver halide photographic light-sensitive material is processed using a developing solution and / or a developing replenisher containing a compound represented by the following general formula (1):
A method for processing a silver halide photographic material as described in any one of the above.

[0018]

Embedded image

In the formula, R ₁ and R ₂ each independently represent a hydroxyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group;
Represents a group of atoms necessary to form a 6-membered ring.

11. The method for processing a silver halide photographic light-sensitive material according to claim 10, wherein the silver halide photographic light-sensitive material is processed using a processing apparatus for a total processing time of 25 seconds or less.

[12] The replenishing amount of the developing solution and / or the replenishing amount of the fixing solution is 200 ml per m ^{2 of the} silver halide photographic material.
12. The method for processing a silver halide photographic light-sensitive material according to 11, wherein the method is processed as follows.

Is achieved.

Hereinafter, the present invention will be described in detail.

The silver halide grains contained in the silver halide emulsion of the light-sensitive material of the present invention are tabular grains having an aspect ratio of 3 to 15 or less, preferably 3 to 8 in at least 50% of the total projected area. . Tabular grains having an equivalent circle diameter of 0.5 μm or more, preferably 0.8 to 2.0 μm.

In the tabular silver halide grains, the aspect ratio means the ratio of the equivalent circle diameter of the main plane to the thickness of the silver halide grains (equivalent circle diameter / grain thickness).

Here, the term "equivalent circle diameter" refers to the equivalent circle diameter when a projected image of a grain is converted into a circular image having the same area, and the grain thickness is defined as two parallel opposite flat silver halide grains. Means the distance between the principal planes. The projected area of a particle can be obtained from the sum of the projected areas of the particles.

The projected particle images for obtaining the total projected area and the particle diameter are as follows. A silver halide crystal sample dispersed on a sample table to such an extent that all the particles do not overlap with each other is obtained by using an electron microscope at a magnification of 10,000 to 5,000. It can be obtained by taking an image at a magnification of 10,000 times and actually measuring the particle diameter or the area at the time of projection on the printed image (the number of measurement is indiscriminately 1000
Or more).

The thickness of the particles can be obtained by observing the sample obliquely with an electron microscope.

A particularly preferred embodiment of the present invention is tabular grains having an aspect ratio of 3 to 15 and an equivalent circle diameter of 0.5 μm or more, and a coefficient of variation of 25% or more, preferably 25 to 35%.

The above-mentioned coefficient of variation is (standard deviation of particles) / (average particle diameter) × 100 = (coefficient of variation) (%) Here, the particle diameter measurement method is to follow the above-mentioned circle equivalent diameter measurement method, The average particle size is a simple average.

[0031] (average particle _{diameter) = Σd i n i / Σn} i as a method of obtaining an emulsion of the present invention, pAg and pH of a water-soluble silver salt and a halide solution into a gelatin solution containing seed grains
Under the control described above, a method obtained by a double jet method can be used. In determining the addition rate, refer to
-48521 and 58-49938 can be referred to.

The silver halide composition of the silver halide emulsion of the present invention contains silver iodide in an amount of 2.0 mol% or less, preferably 0.0 mol% or less.
Either silver iodobromide or silver iodochlorobromide containing 5 to 2.0 mol% may be used.

Regarding the halogen distribution in the grains,
It may have a uniform structure or a layered structure (core / shell structure).

The silver halide emulsion of the present invention may be prepared by any method such as an acid method, a neutral method and an ammonia method, but the double jet method (simultaneous mixing method) is used to react the soluble silver salt with the soluble halide salt. Method).

As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion of the present invention may include a grain forming step by supplying fine silver iodide grains (hereinafter, fine grains). Since the size of the fine particles governs the supply rate of iodine ions, the preferred particle size varies depending on the size and the halogen composition of the silver halide grains of the host, but those having an average equivalent sphere diameter of 0.3 μm or less are used. More preferably, it is 0.1 μm or less. In order for the fine particles to be laminated on the host particles by recrystallization, the particle size of the fine particles is desirably smaller than the sphere equivalent diameter of the host particles, and more preferably 1/10 or less of the sphere equivalent diameter.

The halide composition of the fine grains has a silver iodide content of 95 mol% or more, and is preferably pure silver iodide.

The fine grains are preferably added in a step from the point when the tabular silver halide grains have grown to 90% or more of the finished grains to the start of the desalting step.

In the silver halide emulsion of the present invention, various hydrophilic colloids for containing silver halide as a binder are used. For this purpose, synthetic polymers such as polyvinyl alcohol, polyacrylamide, etc. Photographic binders such as colloidal albumin, polysaccharides, cellulose derivatives and the like may be used.

The silver halide emulsion used in the practice of the present invention has a pA suitable for chemical sensitization by removing a soluble salt by an appropriate method after the completion of the growth of silver halide grains.
For example, a method described in Research Disclosure (RD) 17643 may be used for the flocculation method for removing soluble salts and the noodle washing method, which can be made into g. Illustrative G which is a polymer flocculant described in JP-B-35-16086
And desalting method using G-8 and the like.

Further, (RD) Vol. 102,197
2, October, Item 0208 and Vol. 131,
Desalting may be performed using an ultrafiltration method described in Item 13122, March 1972.

The silver halide emulsion of the present invention has a pBr of 2.5 to 2.5 from the time when the tabular silver halide grains have grown to 90% or more of the finished grains to the start of the desalting step.
The thiocyanate compound is added under the condition of 3.5. After adding 1 × 10 ⁻² to 2 × 10 ⁻¹ mol per mol of silver, the pBr is adjusted to 0.5 to 1.5 by adding a bromide ion, for example, an aqueous potassium bromide solution.
Start desalination.

The thiocyanate compound of the present invention includes
A water-soluble salt such as a metal salt or NH ₄ SCN can be used, but in the case of a metal salt, care should be taken to use a metal element which does not affect photographic performance, and KSCN or NaSCN is preferable. Further, a hardly soluble salt such as AgSCN may be used as fine particles. In this case, the size of the fine particles is preferably 0.02 μm or less in diameter, particularly preferably 0.05 μm or less.

The time of addition of the thiocyanate compound is from the time when 90% or more of the finished tabular grains are grown to the start of the desalting step.

The thiocyanate compound added during grain formation is incorporated into silver halide grains depending on the amount and pBr added. The addition amount is 1 × 10 ⁻⁴ to 2 × 10 ⁻³ mol per 1 mol of the final silver addition amount.

The pBr at the time of addition is particularly important. If it is too low, the rate of incorporation of the thiocyanate compound into the silver halide grains (the ratio of the amount incorporated into the grain surface to the amount of addition) is significantly reduced. It is difficult to bring out sufficient performance. On the other hand, if it is too high, it is known that the uptake rate increases and fog is generated accordingly. Preferably, the uptake rate is 20% or less. For this reason, pBr at the time of adding a thiocyanate compound is preferably 2.5 to 3.5, particularly preferably 2.5 to 3.0.
It is.

The thiocyanate compound which has not been incorporated is preferably removed in the desalting step. However, even in the emulsion after washing with water, the degree of desalting and the p
Depending on the Br, a thiocyanate compound is present in the binder. Since this thiocyanate compound causes fogging with time, its abundance is 1 per mole of silver.
It is preferably from × 10 ^{−4 to} 2 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁰ mol or less per mol of silver,
Particularly preferably, it is 1 × 10 ⁻⁰ mol.

On the other hand, if the amount of the thiocyanate compound present in the grains is too large, fogging is caused. If the amount is too small, the effects during the sensitization and the development are not obtained.

When the pAg is kept at 0.8 or less when forming the particles, the growth amount during that time is preferably 1% or more, more preferably 1% or more of the volume at the time of completion of the particle formation.
It is preferably 0% or more, but as long as the state of pBr 2.5 or more is historyd, the effect is exhibited even during the period when there is substantially no growth of particles. Also, this pBr2.5
In the above state, thiocyanate ions may or may not be present. However, since the incorporation of thiocyanate ions into particles changes with pAg, pBr2.
It is preferable that the formation of particles in the state of 5 or more and the control of pBr for determining the addition and uptake of thiocyanate ion be performed in separate processes.

A method for determining a thiocyanate compound in a light-sensitive material and a silver halide emulsion will be described.

In order to obtain high sensitivity and rapid development progress with good natural aging property, the finally obtained silver halide emulsion or thiocyanate compound in the light-sensitive material is claimed in the present application. It is necessary to control as described in the item. Whether or not the desired state has been achieved can be easily confirmed using a centrifuge and ion chromatography. The equipment used for the measurement conditions is described in Examples.

1. Determination of thiocyanate ion in silver halide emulsion before coating To a silver halide emulsion containing 1.5 × 10 ^-2 mol of silver halide, 10 ml of a 1% aqueous KBr solution was added, and the mixture was added at 40 ° C.
Stir for 0 minutes. This emulsion is centrifuged to completely separate the emulsion, and then the supernatant is diluted 100-fold. After ultrafiltration of the diluent, thiocyanate ions in the diluent are quantified by ion chromatography. For the quantification, a calibration curve previously prepared using an aqueous solution of a thiocyanate compound separately is used.

2. Determination of thiocyanate ion on silver halide grain surface in silver halide emulsion before coating 10 ml of distilled water was added to silver halide emulsion containing 1.5 × 10 ⁻² mol of silver halide, and the mixture was added at 40 ° C. for 30 minutes. Stir. The silver halide emulsion is centrifuged to completely separate the silver halide emulsion, and then the supernatant is diluted 100-fold. After ultrafiltration of the diluent, thiocyanate ions in the diluent are quantified by ion chromatography. For the quantification, a calibration curve previously prepared using an aqueous solution of a thiocyanate compound separately is used. By subtracting the value thus obtained from the value of all thiocyanate ions in the silver halide emulsion previously obtained, the amount of thiocyanate ion adhered to the target grain surface is obtained.

3. Determination of thiocyanate ion in light-sensitive material A silver halide emulsion layer containing 1 g of silver was peeled from the light-sensitive material, and immersed in 49 ml of distilled water. Add this solution to 4
Stir at 0 ° C. for 30 minutes. After the silver halide emulsion is centrifuged, the supernatant is filtered. After diluting the filtered supernatant 10-fold, the contained thiocyanate ion is quantified by ion chromatography. For the quantification, a calibration curve previously prepared using an aqueous solution of a thiocyanate compound separately is used.

4. Determination of thiocyanate ions on the surface of silver halide grains in a light-sensitive material A silver halide emulsion layer containing 1 g of silver is peeled off from the light-sensitive material and immersed in 50 ml of distilled water. Add this solution to 4
Ultrasonic stirring at 0 ° C. for 30 minutes. After the solution is centrifuged, the supernatant is filtered. After diluting the filtered supernatant 10-fold, the contained thiocyanate ion is quantified by ion chromatography.

By subtracting the value thus obtained from the value of the thiocyanate ion in the photosensitive material previously obtained, the amount of the thiocyanate ion adhered to the target particle surface is obtained. Even after performing layer-by-layer peeling even for photosensitive materials with multiple layers applied,
By performing this operation, the adhesion amount of thiocyanate ions in the silver halide emulsion of the target layer can be accurately obtained.

In the case of chemical sensitization, usual sulfur sensitization, reduction sensitization, noble metal sensitization and a combination thereof are used. More specific chemical sensitizers include allylthiocarbamide (Allylthiocarbamide),
Sulfur sensitizers such as thiourea, thiosulfate, thioether and cystine, potassium chloroaurate, auras thiosulfate and potassium chloroparadate (Potassiumchloropaladat)
e) and the like, and reduction sensitizers such as tin chloride, phenylhydrazine and reductone. Further, a selenium compound, a tellurium compound, or the like can be used as a sensitizer.

The silver halide emulsion used in the practice of the present invention may be spectrally sensitized with a cyanine dye or the like. The spectral sensitizing dye may be used alone, or a combination thereof may be used, and the combination of spectral sensitizing dyes is often used particularly for supersensitization.

In the silver halide emulsion of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening of the emulsion.

Compounds that can be used in such a step include, for example, Research Disclosure (RD) 17
No. 643, (RD) 18716 (November 1979)
And (RD) 308119 (December 1989). Table 1 shows the types and locations of the compounds described in these three (RD).

[0061]

[Table 1]

The supports used in the light-sensitive material of the present invention include those described in the above (RD). Suitable supports are plastic films such as polyethylene terephthalate and the like. In order to improve the adhesion of the coating layer, a subbing layer may be provided, or corona discharge or ultraviolet irradiation may be applied. The silver halide emulsion according to the present invention can be coated on both surfaces of the support thus treated.

The light-sensitive material of the present invention may be provided with an antihalation layer, an intermediate layer, a filter layer and the like, if necessary.

In the light-sensitive material of the present invention, a photographic emulsion layer,
Other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. Coating methods include dip coating, roller coating, curtain coating,
An extrusion coating method, a slide hopper method, or the like can be used. For details, see “Coating” in Research Disclosure (RD), Vol. 176, pp. 27-28.
The method described in the section “Procedures” can be used.

The average particle diameter of the phosphor of the fluorescent intensifying screen (hereinafter simply referred to as intensifying screen) used in the image forming method of the present invention is 7
The thickness of less than μm is preferable for preventing the diffusion of light in the phosphor layer which lowers the sharpness, and is more preferably 4 μm or less.
If the average particle size of the phosphor is too small, the sensitivity becomes too low. Therefore, the average particle size is preferably 0.3 μm or more, and more preferably 0.5 μm or more. Here, the average particle diameter means a number average.

The intensifying screen used in the image forming method of the present invention has a binder in a weight ratio of 0.1 to 3.0% based on the weight of the phosphor in the phosphor layer, and disperses the binder in the phosphor. Since the performance is improved, the binder is thinly and uniformly present on the phosphor surface, so that the phosphor particles can approach each other, so that the packing ratio is improved. That is, a phosphor layer with a high filling rate can be obtained without using any means such as compression.

The weight ratio of the binder to the phosphor in the phosphor layer is 0.1 to 3.0%, and the filling rate of the phosphor is 6%.
8% or more, and the thickness of the phosphor layer is 135 to 200 μm
It is.

In general, the phosphor layer is composed of phosphor particles, a binder and voids free of these. Here, the void refers to a space in the phosphor layer in which the phosphor particles and the binder are not substantially present.

Therefore, the volume ratio of the voids in the phosphor layer increases as the amount of the binder decreases. Since this gap acts as a light scattering factor, it prevents diffusion of light emission from the phosphor,
Sharpness can be improved.

When the weight ratio of the binder to the phosphor is 3.0%
When the ratio exceeds 1, the scattering of the light emission is reduced due to the decrease in the gap in the layer, and the light emission is easily diffused, so that the sharpness of the image is deteriorated.

The weight ratio of binder to phosphor is 0.1%
When the value is less than the above range, it is difficult for the binder to widely cover the surface of the phosphor, and it is difficult to perform the intrinsic function of the binder, which binds the phosphors, and it is not possible to obtain a high phosphor filling rate. In addition, the binder is hard to be uniform throughout the entire layer, so that the fluorescent substance is hard to be uniformly present, and the light emission becomes non-uniform, thereby deteriorating the granularity of the image. Further, it is not preferable in that the phosphor layer becomes brittle and easily damaged.

To measure the filling factor of the phosphor in the phosphor layer, the protective layer of the fluorescent intensifying screen was removed, the entire phosphor layer was eluted with an organic solvent, filtered, dried, and then used in an electric furnace. 600
The weight of the phosphor after baking at 1 ° C. for 1 hour to remove the resin on the surface is Og, the thickness of the phosphor layer before elution is Pcm, the area of the intensifying screen used for elution is Qcm ² , and the specific gravity of the phosphor is Rg / cm. ³ and the time is a value calculated by the phosphor filling factor = [O ÷ (P × Q × R ) ] × 100.

Preferred phosphors for use in the intensifying screen of the present invention include the following.

Tungstate phosphors (CaWO ₄ ,
MgWO ₄ , CaWO ₄ : Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor [Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S: T
b, La ₂ O ₂ S: Tb, (Y, Gd) ₂ O ₂ S: Tb,
(Y, Gd) O ₂ S: Tb, Tm, etc.], terbium-activated rare earth phosphate-based phosphor (YPO ₄ : Tb, GdPO ₄ : T
b, LaPO ₄ : Tb, etc.), terbium-activated rare earth oxyhalide phosphor (LaOBr: Tb, LaOB)
r: Tb, Tm, LaOCl: Tb, LaOCl: T
b, Tm, LaOCl: Tb, Tm, LaOBr: T
b, GdOBr: Tb, GdOCl: Tb, etc., thulium-activated rare earth oxyhalide-based phosphor (LaOB)
r: Tm, LaOCl: Tm, etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, BaSO ₄ : Eu ²⁺ , (Ba, S
r) SO ₄ : Eu ²⁺ etc.] divalent europium activated alkaline earth metal phosphate phosphor [Ba ₃ (PO ₄ ) ₂ : Eu
²⁺ , (Ba ₃ (PO ₄ ) ₂ : Eu ^2+, etc.), divalent europium-activated alkaline earth metal fluorinated halide-based phosphor [BaFCl: Eu ²⁺ , BaFBr: Eu ²⁺ , BaFC
l: Eu ²⁺ , Tb, BaFBr: Eu ²⁺ , Tb, BaF
_{2 · BaCl 2 · KCl: Eu} 2+, (Ba · Mg) F 2 ·
BaCl ₂ .KCl: Eu ²⁺ etc.], iodide-based phosphor (C
sI: Na, CsI: Tl, NaI, KI: Tl),
Sulfide phosphor [ZnS: Ag, (Zn, Cd) S: A
g, (Zn, Cd) S: Cu, (Zn, Cd) S: C
u, Al, etc.], a hafnium phosphate-based phosphor (HfP ₂ O ₇ :
Cu, etc.), tantalate-based phosphors [YTaO ₄ , YTa
O ₄ : Tm, YTaO ₄ : Nb, (Y, Sr) Ta
O _4-x : Nb, LuTaO ₄ , LuTaO ₄ : Nb, (L
u, Sr) TaO _4-x : Nb, GdTaO ₄ : Tm, Gd
₂ O ₃ .Ta ₂ O ₅ .B ₂ O ₃ : Tb, etc.] However, the phosphor used in the present invention is not limited to these, and a fluorescent material that emits light in the visible or near ultraviolet region upon irradiation with radiation. Any body can be used.

It is preferable that the fluorescent intensifying screen of the present invention is filled with a phosphor in a gradient particle size structure. In particular, it is preferable to coat large-sized phosphor particles on the surface protective layer side, and to coat small-sized phosphor particles on the support side.
２．０2.0 μm, and those having a large particle diameter are preferably in the range of 10-30 μm.

The binder has a softening temperature or melting point of 30.
A thermoplastic elastomer at ~ 150 ° C is used alone or together with another binder. Since the thermoplastic elastomer has elasticity at room temperature and becomes fluid when overheated, it is possible to prevent the phosphor from being damaged by the pressure during compression. Examples of thermoplastic elastomers are selected from the group consisting of polystyrene, polyolegin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, natural rubber, fluororubber, polyisopropylene, chlorinated polyethylene, styrene-butadiene rubber, and silicone rubber. At least one kind of plastic elastomer.

The mixing ratio of the thermoplastic elastomer in the binder may be from 10% by weight to 100% by weight.
It preferably comprises 0% by weight of a thermoplastic elastomer.

The production of the intensifying screen is as follows. 1. a step of forming a phosphor sheet comprising a binder and a phosphor; Place the phosphor sheet on a support, while compressing at a temperature above the softening temperature or melting point of the binder,
It is preferable that the phosphor sheet is manufactured by a step of bonding the phosphor sheet to a support.

The phosphor sheet serving as the phosphor layer of the intensifying screen is prepared by applying a coating solution in which the phosphor is uniformly dispersed in the binder solution onto a temporary support for forming a phosphor sheet, After drying, it can be manufactured by peeling off from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and the mixture is stirred and mixed to prepare a coating solution in which the phosphor is uniformly dispersed in the binder.

The production of the fluorescent intensifying screen comprises the steps of forming a phosphor sheet comprising a binder and a phosphor, placing the phosphor sheet on a support, and setting the phosphor sheet at a temperature not lower than the softening temperature or the melting point of the binder. It is preferable to manufacture the phosphor sheet in a step of bonding the phosphor sheet to a support while compressing the phosphor sheet.

The phosphor sheet serving as the phosphor layer of the fluorescent intensifying screen is prepared by applying a coating solution in which a phosphor is uniformly dispersed in a binder solution onto a temporary support for forming a phosphor sheet, and drying. Then, it can be manufactured by peeling off from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and the mixture is stirred and mixed to prepare a coating solution in which the phosphor is uniformly dispersed in the binder.

Examples of the solvent for preparing the coating solution include lower alcohols such as methanol, ethanol, n-propanol and n-butanol, hydrocarbons containing chlorine atoms such as methylene chloride and ethylene chloride, acetone, methyl ethyl ketone and methyl isobutyl ketone. And esters of lower fatty acids such as methyl acetate, ethyl acetate and butyl acetate with lower alcohols, ethers such as dioxane, ethylene glycol monoethyl ether and ethylene glycol monomethyl ether, and mixtures thereof.

The mixing ratio between the binder and the phosphor in the coating solution varies depending on the characteristics of the intended fluorescent intensifying screen, the type of the phosphor, and the like. In general, the mixing ratio between the binder and the phosphor is 1: 1.
It is selected from the range of 1-1: 100 (weight ratio), particularly 1:
It is preferable to select from the range of 8 to 1:40 (weight ratio).

In the coating solution, a dispersant for improving the dispersibility of the phosphor in the coating solution, or a bonding agent between the binder and the phosphor in the formed phosphor layer is improved. Various additives such as a plasticizer may be mixed.

Examples of dispersants include phthalic acid, stearic acid, caproic acid, lipophilic surfactants and the like.

Examples of the plasticizer include phosphoric esters such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalic esters such as diethyl phthalate and dimethoxyethyl phthalate; ethyl phthalyl ethyl glycolate; and butyl butyl butyl glycolate. And polyesters of polyethylene glycol and aliphatic dibasic acid, such as polyesters of triethylene glycol and adipic acid, and polyesters of diethylene glycol and succinic acid.

The coating solution containing the phosphor and the binder prepared as described above is uniformly applied to the surface of the temporary support for sheet formation to form a coating film of the coating solution. As this application means, for example, a doctor blade,
It can be performed by using a roll coater, a knife coater, or the like.

As the temporary support, for example, those made of various materials such as glass, wool, cotton, paper, and metal can be used. What can be processed into is preferred. From this point, for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, plastic film such as polycarbonate film, aluminum foil,
Metal sheets such as aluminum alloy foil, general paper and printing base paper such as photographic base paper, coated paper or art paper, baryta paper, resin coated paper, as described in Belgian Patent 784,615. Particularly preferred are processed papers such as paper sized with a suitable polysaccharide, pigment paper containing a pigment such as titanium dioxide, and paper sized with polyvinyl alcohol.

After a coating solution for forming a phosphor layer is applied to the temporary support and dried, the coating solution is peeled off from the temporary support to form a phosphor sheet to be a phosphor layer of a fluorescent intensifying screen. Therefore, it is preferable that a release agent is applied to the surface of the temporary support in advance so that the formed phosphor sheet is easily peeled from the temporary support.

Next, the operation will be described.

A sheet for setting the phosphor formed as described above is prepared. This support can be arbitrarily selected from the materials listed for the temporary support.

Known intensifying screens are provided with an undercoat layer for applying adhesiveness by coating a polymer substance such as gelatin on the surface of the support in order to strengthen the bond between the support and the phosphor layer, or to provide sensitivity and image quality. In order to improve (sharpness and granularity), a light reflecting layer made of a light reflecting material such as titanium dioxide or a light absorbing layer made of a light absorbing material such as carbon black may be provided.

The support used in the present invention can also be provided with these various layers, and the structure thereof can be arbitrarily selected according to the intended intensifying screen, purpose and use.

The phosphor sheet thus obtained is placed on a support, and the phosphor sheet is adhered to the support while being compressed at a temperature not lower than the softening temperature or the melting point of the binder.

In this manner, by utilizing the method of pressing the phosphor sheet on the support without previously fixing it, the sheet can be spread thinly, and not only can the phosphor be prevented from being damaged, but also the sheet can be prevented from being damaged. As compared with the case where the pressure is fixed and pressurized, a high phosphor filling rate can be obtained even at the same pressure.

Examples of the compression apparatus used for the compression processing of the present invention include generally known apparatuses such as a calender roll and a hot press. For example, the compression treatment using a calender roll is performed by placing the phosphor sheet obtained on a support and passing the phosphor sheet at a constant speed between rollers heated to a temperature higher than the softening temperature or melting point of the binder. However, the compression device used in the present invention is not limited to these devices, and may be any device capable of compressing the sheet while heating it. The pressure during compression is 5
It is preferably at least 0 kg / cm ² .

Usually, the intensifying screen is provided with a transparent protective film for physically and chemically protecting the phosphor layer on the surface of the phosphor layer on the side opposite to the side in contact with the support described above. Such a transparent protective film is preferably provided also for the trend intensifying screen of the present invention. The thickness of the protective film is generally 0.1 to 20.
in the range of μm.

The transparent protective layer is formed of a cellulose derivative such as cellulose acetate or nitrocellulose, or a synthetic polymer such as polymethyl methacrylate, polyethylene terephthalate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, or vinyl chloride / vinyl acetate copolymer. Is dissolved in an appropriate solvent, and a solution prepared by coating the solution on the surface of the phosphor layer can be formed.

Alternatively, a plastic sheet made of polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyvinylidene chloride, polyamide, or the like, or a sheet for forming a protective film such as a transparent glass plate is separately prepared and is appropriately bonded to the surface of the phosphor layer. It can be formed by a method such as bonding using an agent.

As the protective layer used in the intensifying screen of the present invention, a film formed by a coating film containing a fluorine resin soluble in an organic solvent is particularly preferable. The fluorine-based resin refers to a polymer of an olefin containing fluorine (fluoroolefin) or a copolymer containing an olefin containing fluorine as a copolymer component. The film formed by the coating film of the fluorine-based resin may be cross-linked. The protective film made of fluorine resin
There is an advantage that dirt such as a plasticizer that comes out of the film or the like when coming into contact with another material or an X-ray film hardly penetrates into the inside of the protective film, so that the dirt can be easily removed by wiping or the like.

When a fluorine-based resin soluble in an organic solvent is used as the material for forming the protective film, this resin was prepared by dissolving the resin in an appropriate solvent. That is, the protective film is formed by uniformly applying a coating liquid for a protective film forming material containing a fluorine-based resin soluble in an organic solvent to the surface of the phosphor layer using a doctor blade or the like, followed by drying. The formation of this protective film may be performed simultaneously with the formation of the phosphor by simultaneous multilayer coating.

The fluorine-based resin is a polymer of a fluorine-containing olefin (fluoroolefin) or a copolymer containing a fluorine-containing olefin as a copolymer component, such as polytetrafluoroethylene, polychlorotrifluoroethylene, or polyfluorene. Examples include ethylene fluoride, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroolein-vinyl ether copolymer.

The fluorine-based resin is generally insoluble in an organic solvent, but a copolymer containing a fluoroolefin as a copolymer component becomes soluble in an organic solvent by a structural unit other than the fluoroolefin to be copolymerized. A protective layer can be easily formed by applying a solution prepared by dissolving in a suitable solvent on the phosphor layer and drying. Examples of such a copolymer include a fluoroolefin-vinyl ether copolymer. Also, polytetrafluoroethylene and its modified products are soluble in a suitable fluorine-based organic solvent such as a perfluoro solvent, and thus are protected by coating in the same manner as the copolymer containing the above-mentioned fluoroolefin as a copolymer component. A film can be formed.

The protective film may contain a resin other than the fluorine-based resin, and may contain a crosslinking agent, a hardener, a yellowing inhibitor and the like. However, in order to sufficiently achieve the above object, the content of the fluorine-based resin in the protective film must be 30% by weight.
It is preferably at least 50% by weight, more preferably at least 70% by weight.

Examples of the resin other than the fluorine resin contained in the protective film include polyurethane resin, polyacryl resin, cellulose derivative, polymethyl methacrylate, polyester, epoxy resin and the like.

Further, the protective film of the intensifying screen of the present invention may be formed from a coating film containing one or both of a polysiloxane skeleton-containing oligomer and a perfluoroalkyl group-containing oligomer.

The polysiloxane skeleton-containing oligomer has, for example, a dimethylpolysiloxane skeleton.
Preferably, it has at least one functional group, for example, a hydroxyl group, and has a molecular weight of 500 to 100,000.
It is preferred that In particular, the molecular weight is 1000 to 100
000, more preferably 300
0 to 10,000. Also, a perfluoroalkyl group,
For example, the oligomer containing a tetrafluoroethylene group or the like desirably has at least one functional group, for example, a hydroxyl group in the molecule, and has a molecular weight of 500 to 1
It is preferably in the range of 00000. In particular, the molecular weight is preferably in the range of 1,000 to 100,000, more preferably 100 to 100,000.

If an oligomer containing a functional group is used, a cross-linking reaction occurs between the oligomer and the protective layer film-forming resin during the formation of the protective film, and the oligomer is incorporated into the molecular structure of the film-forming resin. The oligomer is not removed from the protective film even by long-term repeated use of the intensifying screen or the operation of cleaning the protective film surface, and the effect of adding the oligomer is effective for a long time. Is advantageous.
The oligomer is preferably contained in the protective film in an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 2% by weight.

The protective layer may contain perfluoroolefin resin powder or silicon resin powder. The perfluoroolefin resin powder or the silicon resin powder preferably has an average particle diameter of 0.1 to 10 μm, and particularly preferably has an average particle diameter of 0.3 to 5 μm. These perfluoroolefin resin powders or silicone resin powders are contained in the protective film in an amount of 0.
It is preferably present in an amount of 5 to 30% by weight, more preferably in an amount of 2 to 20% by weight, most preferably in an amount of 5 to 15% by weight.

The protective film of the intensifying screen of the present invention is preferably a transparent synthetic resin layer having a thickness of 5 μm or less formed on the phosphor layer. By using such a thin protective layer, the distance from the phosphor of the intensifying screen to the silver halide emulsion is reduced, which contributes to the improvement of the sharpness of the obtained X-ray image.

The production of the intensifying screen of the present invention is described in JP-A-6-75.
No. 097 can be produced. That is, the materials for the phosphor, the binder, the surface protective layer, the conductive layer, and the steps of manufacturing the combination thereof are preferably manufactured according to the method disclosed in JP-A-6-75097. Further, it is preferable that the phosphor be provided with large-sized particles near the surface protective layer by a multilayer coating method.

In the image forming method of the present invention, the photosensitive material having a silver halide layer on both sides is sandwiched between the intensifying screens and irradiated with X-rays to give imagewise exposure, followed by a developing step and a fixing step. In at least one step, a solid processing agent is supplied, and the photosensitive material is preferably processed while preparing a processing solution. A solid developing replenisher containing a compound represented by the general formula (1) is preferably used as a developing solution. It is preferable to carry out the treatment using

In the general formula (1), R ₁ and R ₂ each independently represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group,
X represents an alkoxycarbonylamino group, a mercapto group, or an alkylthio group, and X represents an atom group necessary for forming a 5- or 6-membered ring.

In the present invention, the compound represented by the general formula (1) is preferably used in an amount of 0.05 to 0.5 mol, more preferably 0.02 to 0.4 mol, per liter of the developing solution. Hereinafter, the compound represented by Formula (1) will be described.

In the general formula (1), R ₁ and R ₂ each independently represent a hydroxy group, a mercapto group or an amino group (substituents are alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl and n- Butyl group, hydroxyethyl group, etc. as substituents), acylamino group (acetylamino group, benzoylamino), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group), alkoxycarbonylamino group (methoxycarbonylamino group,
Ethoxycarbonylamino group), mercapto group, alkylthio group (methylthio group, ethylthio group, etc.).

Preferable examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group. X forms a 5- to 6-membered ring together with two vinyl carbon atoms and a carbonyl carbon atom substituted by R ₁ and R ₂ . These 5
The 6-membered ring may be only a ring itself, or may be a heterocyclic ring containing an oxygen atom or a nitrogen atom in addition to a carbon atom.

As a specific example of the atom group constituting X, -O
_{-, - C (R 3)} (R 4) -, - C (R 5) =, - C (=
O) -, - N (R 6) -, - formed by combining the N =.

Wherein R ₃ , R ₄ , R ₅ and R ₆ are a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (a hydroxy group, a carboxy group or a sulfo group can be mentioned as a substituent), a substituted or unsubstituted aryl group having 6 to 15 carbon atoms (an alkyl group as a substituent) Group, halogen atom, hydroxy group, carboxy group, sulfo group, etc.), hydroxy group and carboxy group.

Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. And preferred 5
Examples of the 6-membered ring include a dihydrofuranone ring, a diclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

The specific examples of the compounds of the present invention are shown below.
The present invention is not limited to this.

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These compounds can be easily obtained as commercial products, or can be easily synthesized by known synthesis methods.

Among the above exemplified compounds, preferred compounds include ascorbic acid and salts thereof (sodium, potassium, lithium salts and the like) and salts of erythorbic acid which is an optical isomer of ascorbic acid.

The content of these lactones in 1 liter of the developing solution is 0.1 mol or more and 2.0 mol or less, more preferably 0.2 mol or more and 0.5 mol or less.

When the amount is 0.1 mol / l liter or more, even if the amount of sulfite is reduced, it is hardly subjected to air oxidation with the passage of time. If the amount is less than 0.1 mol, the decrease in sulfite reduces the developability due to air oxidation.

In the developer used in the present invention, in addition to the compound represented by formula (1), dihydroxybenzenes (for example, hydroquinone) and 3-
Pyrazolidones (eg, 1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-4)
-Aminophenol) and the like can be used alone or in combination. In the developer, for example, a well-known agent such as a preservative, an alkaline agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone agent, a water softener, An agent, a viscosity imparting agent and the like may be used as necessary.

A fixing agent such as thiosulfate and thiocyanate is used in the fixing solution. Further, a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. Other preservatives, pH adjusters,
It may contain a water softener or the like.

In the present invention, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material in response to a demand for reducing the amount of waste liquid. The replenishment amounts of the developing solution and the fixing solution are each 30 to 200 ml per 1 m ^{2 of the} photosensitive material.

The replenishing amount of the developing solution and the replenishing amount of the fixing solution as used herein refer to the amount of the replenishing solution. Specifically, it is the replenishing amount of each of the developing mother liquor and the fixing mother liquor when replenishing the same liquor, and the respective concentrated liquor when the developing concentrated liquor and the fixing concentrated liquor are replenished with a solution diluted with water. And the total amount of water, and the total amount of the solid processing agent volume and water volume when the solid developing agent and the solid fixing agent are replenished with a solution prepared by dissolving in water. And the total volume of the solid processing agent volume and water volume when the solid fixing agent and water are separately replenished. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents, respectively. In particular amount the developer replenisher is 1 m ² per 120ml
In the following cases, the developing replenisher is preferably a liquid or a solid processing agent different from the developing mother liquor in the tank of the automatic developing machine.

In particular, the replenishment rate of the fixing solution is 15 per m ^2.
In the case of 0 ml or less, the fixing replenisher is preferably a liquid or a solid processing agent different from the fixing mother liquor in the tank of the automatic processor, and the amount of thiosulfate contained in the fixing replenisher is included in the fixing mother liquor. It is preferred that the amount is larger than the amount given.

In the present invention, it is preferable to use the solid processing agent developer and the fixing agent dissolved in water.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

The light-sensitive material of the present invention is continuously processed using a solid processing agent. The solid processing agent referred to here is a solid processing agent such as a powder processing agent, a tablet, a pill, and a granule, which is subjected to moisture proof processing as necessary. The powder is an aggregate of fine crystals, and the granule is a powder obtained by adding a granulation step to a powder, and refers to a granular material having a particle size of 50 to 5000 μm.
A tablet means a powder or a granule obtained by compression molding into a certain shape.

To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily molded photographic processing agent. Any means can be adopted such as forming a coating layer by spraying.

A preferred tablet production method is a method in which a powdered solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity, handling properties or dust when used on the user side, cylindrical, so-called tablets are used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

The bulk density of the solid processing agent is preferably 1.0 g / cm ³ or more in the case of a tablet from the viewpoint of solubility and effect.
2.5 g / cm ³ is preferred. When it is more than 1.0 g / cm ³ , the strength of the obtained solid is preferable,
When the diameter is smaller than ³ cm ³ , the solubility of the obtained solid is more preferable. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

Solid processing agents are used in photographic processing agents such as developers, fixing agents, and rinsing agents. Developers have a great effect of the present invention, especially the effect of stabilizing photographic performance.

The solid processing agent used in the present invention falls within the scope of the present invention in that only one part of a certain processing agent is solidified, but preferably all the components of the processing agent are solidified. It is. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

It is preferable that at least one of the development and fixing steps is carried out in accordance with the processing amount information while all the processing agents to be replenished into the processing tank are charged as solid processing agents. Therefore, when replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water.

In other words, when there are two or more types of processing tanks requiring replenishment, one tank for storing the replenishing liquid by sharing the replenishing water is sufficient, and the size of the automatic developing machine can be reduced. I can do it.

The replenishing water tank may be provided externally or may be built in an automatic developing machine, and is preferably built in from the viewpoint of space saving and the like.

When the developing replenisher is solidified, all of the alkali agent and the reducing agent are converted into solid processing agents, and in the case of tablets, at least three agents are used, and most preferably one agent is used.
This is a preferred embodiment of the solid processing agent used in the present invention. When a solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

In the present invention, the solid processing agent developer and the fixing agent can be dissolved in water.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

In the present invention, processing is carried out using an automatic developing machine because of a demand for shortening the developing time. Regarding the processing time, it is preferable that the total processing time (Dry to Dry) from when the leading end of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 25 seconds or less.

The term "total processing time" as used herein includes the total processing time required for processing a black-and-white photographic light-sensitive material, and specifically, for example, the steps such as development, fixing, washing or rinsing, and drying necessary for processing. Time including all of the above, that is, Dry to
It is the time of Dry.

The replenishing amount of the fixing solution in the processing method of the present invention is 100 ml or more and 300 ml or less per 1 m ^{2 of} the photosensitive material. The thiosulfate ion concentration in the fixing solution is 1.3 to 2.0 mol / l.

In the processing method according to the present invention, it is preferable to use a starter for the developer. The starter is an acidic additive and may be either an organic acid or an inorganic acid, or may be a mixture.

The starter may be a solid or a solution as long as it is soluble in a developing solution, and is preferably used in a solution state. Specific components of the starter include, for example, acetic acid, citric acid, boric acid, sulfuric acid, salicylic acid, and salts thereof.

These acids can be used alone or in combination of two or more. The amount of the starter added is 0.1 to 100 g, preferably 0.5 to 50 g, per liter of the developer.

The width of decrease in developer pH due to the addition of the starter is preferably 0.2 or more, more preferably 0.2 to 1.0.

The starter may contain components other than the acid, and in particular, may contain components such as alkali halides and hydroquinone monosulfonate which increase in the development reaction. Potassium bromide, potassium chloride, etc. are used as alkali halides.
0.1 to 10 g per liter is preferred.

It is also preferable to add a starter to the fixing solution. In this case, it is preferable to add an alkali to bring the pH closer to the running state.

The photosensitive material which has been subjected to the developing and fixing processes is subsequently washed with water and then dried through a drying step.

When washing with a small amount of water, it is more preferable to provide a washing tank for a squeeze roller. Further, in order to reduce the pollution load which becomes a problem when washing with a small amount of water, addition of various oxidizing agents or filtration with a filter may be combined. Further, by replenishing the washing or stabilizing bath with water subjected to antifungal means in accordance with the treatment, part or all of the overflow liquid generated from the washing or stabilizing bath is disclosed in JP-A-60-2.
As described in JP-A-35133, it can also be used for a processing solution having a fixing ability, which is a preceding processing step.

In addition, the treatment agent component which is likely to be generated when washing with a small amount of water and which prevents water bubble unevenness and / or adheres to the squeeze roller,
A water-soluble surfactant or an antifoaming agent may be added to prevent transfer to the treated film. In addition, a dye adsorbent may be provided in a washing tank to prevent contamination by dyes eluted from the silver halide photographic light-sensitive material, and a stabilization treatment may be performed following the washing treatment. 2-201357, 2-132435,
A bath containing the compounds described in JP-A-1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent whitening agent, various chelating agents, a film pH regulator, a hardening agent, a disinfectant,
Fungicides, alkanolamines and surfactants can be added.

Water used in the washing step or the stabilizing step includes tap water, deionized water, halogen, an ultraviolet germicidal lamp, and various oxidizing agents (ozone, hydrogen peroxide,
For example, water sterilized by chlorate or the like can be used.

[0163]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of emulsion EM-A) 37 g of silver nitrate aqueous solution (4.00 g of silver nitrate) and potassium bromide were placed in a vessel kept at 55 ° C. by adding 6 g of potassium bromide and 7 g of gelatin to 1 liter of water. The aqueous solution (potassium bromide or 5.9 g) was added by stirring by a double jet method for 37 minutes. Next, 70
After 18.5 g of gelatin was added while the temperature was raised to ° C., an aqueous solution of silver nitrate was added to adjust pBr. These are described in Table 1 as pBr during the particle formation process.

Here, 7 ml of a 25% aqueous ammonia solution was used.
After addition of WO and physical aging for 10 minutes at the same temperature, 6.5 ml of a 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by a controlled double jet method while maintaining pBr.

When the finished particles grew as shown in Table 1, pB
After adjusting r, an aqueous solution of potassium thiocyanate and fine silver iodide particles were added. Table 1 shows the amount, timing, and pBr at the time of addition. Five minutes later, after physical ripening at the same temperature, pBr for desalting as shown in Table 1 was removed, and then soluble salts were removed by a precipitation method.

The emulsion was heated to 40 ° C. and gelatin 30
g and phenoxyethanol 2.4 g were added, and the pH was adjusted to 5.90 using a sodium hydroxide solution, and the pAg was adjusted to 8.21 using a silver nitrate solution or potassium bromide.

These emulsions were stirred and kept at 50 ° C. to perform chemical sensitization. First, a dispersion of solid fine particles was added to the following spectral sensitizing dye (A) so as to be 460 mg per mole of silver, and then 7.0 × 10 ^-4 mole of ammonium thiocyanate was added per mole of silver, and chloroauric acid was added. Potassium, sodium thiosulfate, and triphenylphosphine selenide were added in an amount of 3.0 × 10 ⁻⁶ mol per mol of silver to perform optimal chemical ripening.

Further, a silver iodide fine grain emulsion described later was mixed with silver 1
After addition of 3.0 × 10 ⁻³ mol per mol, the mixture was stabilized with 3.0 × 10 ⁻⁶ mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI), and emulsion EM was added. −
A was obtained.

Table 1 shows the shape of the grains and the amount of thiocyanate ions incorporated in the grains of the obtained emulsion EM-A.

(Preparation of Spherical Sensitizing Dye Solid Fine Particle Dispersion) Spectral sensitizing dyes (A) and (B) were added at a ratio of 100: 1 to water previously adjusted to 27 ° C., and a high-speed stirrer ( (Dissolver) at 3.500 rpm for 30 to 120 minutes to obtain a solid particulate dispersion of the spectral sensitizing dye.

At this time, when the concentration of the spectral sensitizing dye (A) was 2
%.

Spectral sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (2-sulfopropyl)
Anhydrous oxacarbocyanine sodium salt Spectral sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolo Anhydrous carbocyanine sodium salt (Preparation of silver iodide fine particles) Solution A ₁ Ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water Solution B ₁ Silver nitrate 360 g Make up to 605 ml with distilled water Solution C ₁ KI 352 g Distilled water in solution a ₁ was added to the reaction vessel in 605 ml, with stirring maintained at 40 ° C., the solution B ₁ and solution C ₁ was added a constant speed over a period of 30 minutes by a simultaneous mixing method. The pAg during the addition was kept at 13.5 by a standard pAg control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average particle size of 0.06 μm. This emulsion is referred to as a silver iodide fine grain emulsion.

(Preparation of Coated Sample) Synthesis of Colloidal Tin Oxide Sol Dispersion A uniform solution prepared by dissolving 65 g of stannic chloride hydrate in 2000 ml of distilled water was boiled to obtain a coprecipitate. The formed coprecipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed, and it is confirmed that there is no reaction of chloride ions.
After adding and dispersing this precipitate in 1000 ml of distilled water,
The total volume is 2000 ml. Further, 40 ml of 30% ammonia water is added, and the mixture is heated in a water bath to form a tin oxide sol solution.

When used as a coating liquid. The sol solution is concentrated to about 8% while blowing ammonia gas into the sol solution. Regarding the volume resistivity of the particles contained in this sol solution, a thin film was formed on silica glass using the sol solution, and the value measured by the four probe method was defined as the volume resistivity of the particles. The measured volume resistivity is 3.4 ×
It was 10 ⁴ Ωcm.

(Preparation of Tin Oxide Sol Subbed Support)
Next, a polyethylene terephthalate film base (thickness: 175 μm) for X-rays colored blue with a concentration of 0.17
Was subjected to a corona discharge treatment of 0.5 kV · A · min / m ^{2 on} one side of the undercoating, and then the undercoat latex liquid shown in the following (L-2) was dried to a thickness of 0.2 μm by the following ( L
-1) was sequentially applied so that the film thickness after drying became 0.053 μm, and dried at 123 ° C. for 2 minutes.

(L-1) C ₆ H ₅ —CH ₂ —CH ₂ —CH (COONa) —CH ₂ C
OONa C ₆ H ₅ —CH ₂ —CH ₂ —CH (COONa) —CH
_{2 (COOCH 2 -CF 2 CF 2} H (L-2) n- butyl acrylate 10 wt%, t-butyl acrylate 35 wt%, styrene 27 wt%, and 2-hydroxyethyl acrylate 28 wt% of the copolymer latex solution (30% solids).

In the lower layer on the other side of the same support, the tin oxide sol synthesized above, the above solution (L-2) and the following solution (L-4) were mixed at a volume ratio of 35:15:50. The coating liquid was applied to the upper layer so that the film thickness after drying was 0.20 μm and the amount of the sol component applied was 400 mg / m ^2.
A coating solution obtained by mixing 1) and the following (L-3) solution at a volume ratio of 70:30 was simultaneously applied so that the film thickness after drying was 0.053 μm, and dried at 120 ° C. for 1 minute. Before application, a corona discharge treatment of 0.5 kV · A · min / m ² was performed.

(L-3) Dimethyl terephthalate 34.0
2 parts by weight, 25.52 parts by weight of dimethyl isophthalate, 5
-12.97 parts by weight of dimethyl sodium sulfoisophthalate, 47.85 parts by weight of ethylene glycol, 1,4-
18.95 parts by weight of cyclohexanedimethanol, 0.065 parts by weight of calcium acetate monohydrate, and 0.022 parts by weight of manganese acetate tetrahydrate were added in a nitrogen stream at 170 to 220 parts by weight.
After performing transesterification while distilling off methanol at ℃, 0.04 parts by weight of trimethyl phosphate, 0.04 parts by weight of antimony trioxide as a polycondensation catalyst and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid. And add 22
At a reaction temperature of 0 to 235 ° C., almost the theoretical amount of water was distilled off to carry out esterification. Thereafter, the pressure inside the reaction system was further reduced and the temperature was raised over about 1 hour, and finally polycondensation was performed at 280 ° C. and 1 mmHg or less for about 1 hour to obtain a polyester polymer having an intrinsic viscosity of 0.35.

6. Aqueous solution of the obtained polyester polymer
30 g of styrene and 30 of butyl methacrylate in 330 g
g, glycidyl methacrylate 2 g, acrylamide 2
0 g and 1.0 g of ammonium persulfate at 80 ° C.
For 5 hours, and cooled to room temperature to reduce the solid content to 10% by weight.
To obtain a coating solution.

(L-4) A copolymer latex liquid containing 40% by weight of n-butyl acrylate, 20% by weight of styrene, and 40% by weight of glycidyl methacrylate.

(Synthesis of Composite Latex Lx-1) 100
A stirrer, thermometer, dropping funnel, nitrogen inlet tube, and reflux condenser were attached to a 0 ml four-necked flask. While introducing nitrogen gas and performing deoxidation, 360 ml of distilled water and 126 g of 30 parts by weight of a colloidal silica dispersion were added, and the mixture was heated until the internal temperature reached 80 ° C., and 1.3 g of the following surfactant:
And ammonium persulfate 0.023 as an initiator.
g of vinyl pivalate and then 12.6 g of vinyl pivalate were added and reacted for 4 hours. Thereafter, the mixture was cooled and adjusted to pH 6 with a sodium hydroxide solution to obtain a composite latex Lx-1.

[0183]

Embedded image

The latex Lx-1 is composed of inorganic compound: hydrophobic latex = 4: 1.

The following coating solution for the transverse light-shielding layer, the coating solution for the emulsion and the coating solution for the protective layer were simultaneously coated on both sides of the undercoated support so as to have the following coating amounts, respectively.
Dried.

First layer (transverse light shielding layer) Gelatin 0.2 g / m ² Solid fine particle dispersion dye (AH) 20 mg / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (emulsion layer) Emulsion EM-A obtained above The following various additives were added.

Gelatin (including the content in emulsion EM-A) 1.2 g / m ² Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5 - triazine 5 mg / m ² t-butyl - catechol 5 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 20mg / m ² styrene - sodium maleic anhydride copolymer 80 mg / m ² of polystyrene sulphonic acid 80 mg / m ² trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 1 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 50 mg / m ² Sodium ² -mercaptobenzimidazole-5-sulfonate 5 mg / m ² compound (H) 0.5 mg / m ² _{n-C 4 H 9 OCH 2} CH (OH) CH 2 N (CH 2 COOH) 2 20mg / m 2 Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 g / m ² Compound (P) 0.2 g / m ² Compound (Q) 0.2 g / m ² Hydrophobic latex Lx-1 1.2 g / m ² (latex component amount) (0.3 g / m ² ) Water-soluble polymer (molecular weight 50,000) Dextran) 0.3 g / m ² Leuco compound (R) 2 × 10 ⁻³ mol / mol Ag Third layer (lower layer of protective layer) Gelatin 0.3 g / m ² Matting agent composed of polymethyl methacrylate (area average particle size) 7.0μm) 27mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5 - triazine sodium salt 10 mg / m ² polysiloxane (SI) 50mg / m ² compound ( ) 30 mg / m ² Compound (S-1) 7mg / m 2 Compound (K) 15mg / m ² hardener (B) 2mg / m ² Compound (J) 2mg / m ² Compound (O) 50mg / m ² Compound (S-2) 5 mg / m ²

[0188]

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[0189]

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[0190]

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[0191]

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The amount of each material was the amount per one side, and the amount of silver applied was adjusted so as to be 1.5 g / m ² per side. Tables 1 and 2 were prepared.
The results are shown in Table 3.

[0193]

[Table 2]

[0194]

[Table 3]

(Production of Fluorescent Intensifying Screen 1) Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Binder polyurethane thermoplastic elastomer (Demolac TPKL-5-2625 solid content 40% Sumitomo Bayer 20 g nitrocellulose (digestion degree: 11.5%) 2 g A methyl ethyl ketone solvent was added to the above and dispersed with a propeller type mixer to prepare a coating solution for forming a phosphor layer having a viscosity of 25 ps (25 ° C.) ( Binder / phosphor ratio = 1/2
2).

Separately, as a coating solution for forming an undercoat layer, 90 g of a soft acryl resin solid content and 50 g of nitrocellulose were used.
Is added with methyl ethyl ketone, dispersed and mixed to obtain a viscosity of 3 to 3.
A 6 ps (25 ° C.) dispersion was prepared.

Thickness of 250 μm with kneaded titanium dioxide
Polyethylene terephthalate base (support) was placed horizontally on a glass plate, and the coating solution for forming an undercoat layer was uniformly applied to the support using a doctor blade.
The coating film was dried by gradually raising the temperature from 100 ° C. to 100 ° C. to form an undercoat layer on the support. The thickness of the coating film is 15μ
m.

The above-mentioned coating solution for forming a phosphor layer was uniformly coated thereon with a doctor blade to a thickness of 240 μm and dried, and then compressed. Compression was performed using a calender roll at a pressure of 800 kgw / cm ² and a temperature of 80 ° C. After this compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example [1] of JP-A-6-75097.

As described above, a fluorescent intensifying screen 1 comprising a support, an undercoat layer, a phosphor layer and a transparent protective layer was produced.

(Manufacture of Fluorescent Intensifying Screen 2) In the manufacture of the fluorescent intensifying screen 1, the same procedure as in the fluorescent intensifying screen 1 was performed except that the thickness of the coating solution for forming the phosphor layer was applied at 150 μm and no compression was performed. Thus, a fluorescent intensifying screen 2 comprising a support, an undercoat layer, a phosphor layer, and a transparent protective layer was produced.

(Measurement of Characteristics of Fluorescent Intensifying Screen) 1) Measurement of Sensitivity A fluorescent intensifying screen to be measured is placed on an MRE single-sided photosensitive material manufactured by Eastman Kodak Co., Ltd. The fluorescent intensifying screen is placed in contact with
The line exposure was changed, and step exposure was performed with a width of logE = 0.15. The exposed true photosensitive material was subjected to a development process by the method described in Measurement of Characteristics of Photosensitive Material to be described later to obtain a measurement sample.

For the measurement sample, the concentration was measured with visible light to obtain a characteristic curve. The sensitivity is represented by the reciprocal of the amount of X-ray exposure for obtaining Dmin + density of 1.0.
(Reference value) and expressed as relative sensitivity.

2) Measurement of X-ray absorption The intrinsic filtration operated at 80 kVp with three-phase power supply allowed the sample fluorescent screen fixed at a position 200 cm from a tungsten anode equivalent to an aluminum plate of 2.2 mm to be fixed at a position of 200 cm. Then, the X-ray dose transmitted through the intensifying screen was measured at a position 50 cm after the phosphor layer of the fluorescent intensifying screen using an ionizing dosimeter to determine the amount of X-ray absorption. The X-ray dose at the measurement position measured without passing through the fluorescent intensifying screen was used as a reference.

The results obtained are summarized in Table 4.

[0205]

[Table 4]

Processing 1 (Development Using a Solid Processing Agent Containing Hydroquinone) A developing (replenishing) tablet was prepared according to (A) and (B). The tablet for replenishment is the same as the tablet for development.

Operation (A) Preparation of Tablet A 3000 g of hydroquinone, a developing agent, is ground in a commercially available bantam mill until the average particle size becomes 10 μm. 3000 g of sodium sulfite and 20 g of potassium sulfite are added to this fine powder.
00 g and 1000 g of Dimezone S (1-phenyl-4-hydroxymethyl-4-methylpyrazolidone) were added, mixed in a mill for 30 minutes and mixed in a commercially available stirred granulator at room temperature for about 10 minutes at 30 ml. After granulating by adding water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to almost completely remove the moisture of the granulated material. 100 g of polyethylene glycol 6000 was uniformly mixed with the thus-prepared granules in a room conditioned at 25 ° C. and 40% RH or less for 10 minutes using a mixer, and the obtained mixture was mixed with Kikusui 1527H Tough Presto Collect
U was modified with a tableting machine to reduce the filling amount per tablet to 3.8.
The tablet was compressed to 4 g, and compression tableting was performed to produce 2500 developing (replenishing) tablets A.

Operation (B) Preparation of Granulated Material (B) 100 g of sodium diethylenetriaminepentaacetate, 4000 g of potassium carbonate, 5-methylbenzotriazole 1
0 g, 1-phenyl-5-mercaptotetrazole 7
g, 2-mercaptohypoxanthine 5 g, potassium hydroxide 200 g, and N-acetyl-D, L-penicillamine are ground and granulated in the same manner as in the operation (A). The amount of water added is 30.
After granulation, the mixture is dried at 50 ° C. for 30 minutes to remove the moisture of the granules almost completely. The mixture obtained in this manner was used as a tough pre-stress collect 152 manufactured by Kikusui Seisakusho.
7HU was converted to a tableting machine with a filling amount of 1.73 g per tablet using a modified tableting machine to produce 2500 tablets (for replenishment) of tablets B for compression.

Next, a fixing agent (replenishment) tablet was prepared by the following procedure. The fixing and the replenishment are the same.

Next, a fixing (replenishing) tablet was prepared in the following manner. The fixing and the replenishment are the same.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, granulation is performed in the same manner as in the operation (A) with the addition amount of water being 500 ml. After granulation, the granulated
Dry at 30 ° C. for 30 minutes to remove almost completely the water content of the granulated material. 4 g of sodium N-lauroylalanine is added to the granules thus prepared, and the mixture is uniformly mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho with the filling amount per tablet set to 6.202 g, and
2500 developing (replenishing) tablets C were prepared.

Operation (D) Boric acid 1000 g, aluminum sulfate 18 hydrate 1500
g, sodium hydrogen acetate (3000 g, dried by mixing equimolar glacial acetic acid and sodium acetate), tartaric acid 2
00g is ground and granulated in the same manner as in the operation (A). After adding water to 100 ml and granulating, the granulated material is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. After adding 4 g of N-lauroylalanine sodium to the granules thus prepared and mixing for 3 minutes, the obtained mixture was subjected to Kikusui Seisakusho's Tough Presto Collect 1527HU.
Using a modified tableting machine to increase the filling amount per tablet to 4.56.
The tablet was compressed and compressed to 2 g, and 1250 fixing (replenishing) tablets D were prepared.

Developer Starter Composition Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1000 ml The developer was prepared by dissolving and diluting 434 developing tablets A and B with water at the start of processing (start of running). Then 1
The volume was adjusted to 6.5 liters, 330 ml of a starter was added, and the mixture was filled in a developing tank as a starting solution to start processing.

The light-sensitive material prepared above was exposed to light so that the optical density after the development processing became 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 equipped with a charging portion for a solid processing agent and modified so as to process at a processing speed of 15 seconds was used. During the running, the developer was added with the above-mentioned ^two agents A and B per 0.62 m ² of the photosensitive material and 76 ml of water (replenishment amount: 122.6 ml / m ² ).

The pH of Agent A and Agent B when dissolved in 38 ml of water was 10.70. The fixing solution was one and water two and D agent a photosensitive material 0.62 meters ² per the C agent was added 74 ml (replenishment rate 119.3ml / m ^2). The rate of addition of water to each treating agent started almost simultaneously with the addition of the treating agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the treating agent.

Processing conditions Developing time 4 seconds Fixing time 3.1 seconds Rinse time 2 seconds Rinse and dry (squeeze) 1.6 seconds Drying time 4.3 seconds Total processing time 15 seconds Processing 2 (solid processing not containing hydroquinone) Developing process using an agent) Hydroquinone-free developing (replenishing) tablets were prepared according to the following operations (E) and (F). The development and replenishment are the same.

Operation (E) 13,000 g of sodium erythorbate as a developing agent is ground in a commercially available bantam mill until the average particle diameter becomes 10 μm. To this fine powder, 4877 g of sodium sulfite, 975 g of phenidone, and 1635 g of DTPA were added.
After mixing for 0 minutes and granulating by adding 30 ml of water at room temperature for about 10 minutes in a commercially available stirred granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier. The water in the granulated material is almost completely removed. To the granules thus prepared was added 2167 polyethylene glycol 6000.
g, in a room humidified to 25 ° C. and 40% RH or less, and uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH. 8.715 g per tablet
And compression and tableting for 2500 development (for replenishment)
Tablet E was prepared.

Operation (F): 19500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, sodium hydrogencarbonate
25 g, glutaraldehyde sulfite adduct 650 g, polyethylene glycol 6000 1354 g operation (A)
Grind and granulate in the same manner as described above. The amount of water to be added is 30.0 ml, and after granulation, the granulated material is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture obtained in this manner was treated with Tough Presto Collect 1527 manufactured by Kikusui Seisakusho.
3. The filling amount per tablet was adjusted by a tableting machine with modified HU.
Compressed tableting was performed at 562 g to prepare 1250 fixing (supplementing) tablets F.

Next, a fixing (replenishing) tablet was prepared by the following procedure. The fixing and the replenishment are the same.

Operation (G) 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite and 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate were pulverized and granulated in the same manner as in operation (A). The amount of water to be added is 500 ml, and after granulation, the granulated material is dried at 60 ° C. for 30 minutes to substantially completely remove the water content of the granulated material. The tableting machine obtained by converting the thus obtained granulated product Tough Press Collect 1527HU manufactured by Kikusui Seisakusho into a tableting machine with a filling amount per tablet of 8.214 g was subjected to compression tableting, and 2500 fixing (replenishment) was carried out. A) Tablet G was prepared.

Operation (H) 1860 g of boric acid, aluminum sulfate 18 hydrate 6500
g, glacial acetic acid 1860 g, and sulfuric acid (50 wt%) 928 g are pulverized and granulated in the same manner as in the operation (A). Add water to 10
After the granulation, the mixture is dried at 50 ° C. for 30 minutes to remove the moisture of the granulated product almost completely. The mixture obtained in this manner was treated with Tough Presto Collect 1527 manufactured by Kikusui Seisakusho.
3. The filling amount per tablet was adjusted by a tableting machine with modified HU.
The tablet was compressed to 459 g and compression tableting was performed to prepare 2500 fixing (supplementing) tablets H.

Developer Starter Composition Glacial acetic acid 210 g KBr 350 g Water was added to make 1000 ml The developer was prepared by dissolving and diluting 1650 tablets E for development and 825 tablets F for water at the start of processing (start of running). The volume was adjusted to 16.5 liters, 330 ml of a starter was added, and the mixture was filled in a developing tank as a starting solution to start processing.
The pH of the developer to which the starter was added was 10.45.
Met.

The photosensitive material prepared above was exposed to light so that the optical density after the development processing became 1.0, and running was performed. For the running, an automatic developing machine SRX-502 (manufactured by Konica Corporation) which was equipped with a solid processing agent and was modified so as to be able to process at a processing speed of 25 seconds was used. During running, the developer contains one E agent, two F agents and 20 ml of water per 1.00 m ² of the photosensitive material (replenishment amount 20 ml).
ml / m ² ).

The pH when each of the agent E and the agent F was dissolved in 20 ml of water was 10.70. The fixing solution was added with four of the above G agents, two of the H agents and 50 ml of water (replenishment amount: 50 ml / m ² ) per 1.00 m ² of the photosensitive material. The water addition rate for each treatment agent starts at almost the same time as the treatment agent addition and is approximately 10% in proportion to the dissolution rate of the treatment agent.
Minutes at a constant speed.

Processing Conditions Developing time 4 seconds Fixing time 3.1 seconds Rinse time 2 seconds Rinse and dry (squeeze) 1.6 seconds Drying time 4.3 seconds Total processing time 15 seconds Processing 3 (general formula not containing hydroquinone) (Development processing using solid processing agent containing compound of (1)) Processing liquid is processing 2
Was prepared in the same manner as in Treatment 2, except that the exemplified compound A-1 of the general formula (1) was used in an equimolar amount in place of sodium sorbate in the above.

(Evaluation of Sensitometry) The fluorescent intensifying screens 1 of each of the obtained samples were allowed to stand naturally at room temperature (20 ° C.) for 3 days, and as a forced deterioration test, left at 50 ° C. and 80% humidity for 3 days. Or, after irradiating X-rays through a penetrometer type B (manufactured by Konica Medical Co., Ltd.), an automatic developing machine SRX-701 (manufactured by Konica Corporation)
Tables 5 and 6 show the results of measuring the sensitivity of each of the treatment agents with the replenishing amount and the treatment time under the above conditions.

Here, the sensitivity of each sample is calculated by calculating the reciprocal of the X-ray exposure amount required to obtain the minimum density +1.0 when the sample 1 is exposed between the fluorescent intensifying screens 1 and processed in the process 1. To 100
As relative values at the time.

At the start of the processing of the developing solution (start of running), each of the A agent and the B agent of the developing solution replenishing tablet was added by 4 parts.
Thirty-four were dissolved and diluted with water, and a liquid obtained by adding 330 ml of a starter to 16.5 liters was used as a starting liquid to fill a developing tank and start processing. The pH of the developer to which the starter was added was 10.45.

Developer Starter Composition Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make up to 1000 ml.
The fixing bath was filled with 11.0 liters of a fixing solution prepared by dissolving 8 g of the agent and 149 g of the D agent in water.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. During the running, each processing was carried out by adding two of the above-mentioned agents A and B and 76 ml of water per 0.62 m ² of the photosensitive material to the developing solution.

The pH of each of Agent A and Agent B when dissolved in 20 ml of water was 10.70. To the fixing solution, ^two C agents, one D agent and 74 ml of water were added per 0.62 m ² of the photosensitive material. The rate of addition of water to each treating agent started almost simultaneously with the addition of the treating agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the treating agent.

[0232]

[Table 5]

[0233]

[Table 6]

Tables 2, 3, 4, 5 and 6 show that the emulsion production method, photographic material, processing method and X-ray image forming method of the present invention show low fog, high sensitivity and storage stability with time (fog, sensitivity). It can be seen that the composition has good aptitude and rapid processing suitability.

[0235]

According to the present invention, a light-sensitive material having low fog, high sensitivity, good storage stability over time (fog, sensitivity), and excellent rapid processing suitability, a processing method therefor, a method for producing an emulsion, and an X-ray image forming method was gotten.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/26 G03C 5/26 520 520 5/30 5/30 5/31 5/31 5/395 5/395 G21K 4/00 G21K 4/00 A

Claims (12)

[Claims] (1) 50% of the total projected area of a silver halide emulsion
The above are the tabular grains having an aspect ratio of 3 to 15, and the tabular grains are grown from 90% or more of the finished grains to the start of the desalting step under the conditions of pBr 2.5 to 3.5. 1 × 10 ^-2 thiocyanate compound per mole of silver
After adding ~ 2 x 10 ^-1 mol, pBr was added to 0.5 to 1.5
And a method for producing a silver halide photographic emulsion. 2. The silver halide photographic emulsion according to claim 1, wherein silver iodide fine grains are added in a step from the point when the finished grains are grown by 90% or more to the start of a desalting step. Production method. 3. The method for producing a silver halide photographic emulsion according to claim 1, wherein the pBr in the grain growth step up to 90% with respect to the finished grains is 1.0 to 2.5. . 4. A silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support, wherein the silver halide photographic emulsion according to claim 1 or 2 is incorporated in the emulsion layer. A silver halide photographic light-sensitive material characterized by being contained. 5. The content of the thiocyanate compound present on the surface of silver halide grains is 1 × 10 ^-4 to 2 per mol of silver.
5. The silver halide photographic light-sensitive material according to claim 4, wherein the amount is ^10-3 mol. 6. The silver halide photographic light-sensitive material according to claim 4 or 5, wherein the silver halide photographic light-sensitive material has a photosensitive emulsion layer on both sides.
X-rays exhibiting an absorption amount of 45% or more with respect to X-rays having a line energy of 80 kVp, a filling rate of the phosphor of 68% or more, and a phosphor intensifying screen having a thickness of 135 to 200 μm. An X-ray image forming method, wherein imagewise exposure is performed by irradiation. 7. A processing method for a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 4 is processed in a processing step including a developing step and a fixing step. 8. A silver halide photographic material is processed in at least one of a developing step and a fixing step by supplying a solid processing agent and preparing a processing solution.
The method for processing a silver halide photographic light-sensitive material described in 1 above. 9. The processing method for a silver halide photographic material according to claim 8, wherein the processing is performed by a processing apparatus having a mechanism for supplying a solid processing agent to the processing layer. 10. The method according to claim 7, wherein the silver halide photographic material is processed using a developing solution and / or a developing replenisher containing a compound represented by the following general formula (1).
10. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 9. Embedded image In the formula, R ₁ and R ₂ each independently represent a hydroxyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group, and X forms a 5- to 6-membered ring Represents the group of atoms required to perform 11. The processing method for a silver halide photographic light-sensitive material according to claim 10, wherein the silver halide photographic light-sensitive material is processed using a processing apparatus for a total processing time of 25 seconds or less. 12. The silver halide photographic light-sensitive material according to claim 11, wherein the replenishment amount of the developing solution and / or the replenishment amount of the fixing solution is processed at 200 ml or less per m ^{2 of the} silver halide photographic light-sensitive material. Processing method.