JPH1195351A - Medical photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical photographic sensitive material prevented from occurrence of uneven development and inferior development and poor fixation in the case of rapid and low-replenished processing without deteriorating pressure resistance by incorporating saponine and dextran in a hydrophilic colloidal layers including a photosensitive layer formed on both sides of a transparent support. SOLUTION: The hydrophilic colloidal layers including the photosensitive layer are formed on both sides of the transparent support and they contain the saponine and dextran. The photosensitive material containing the saponine and the dextran is processed with a developing solution and a fixing solution both containing no boric acid and a compound having a Ca-chelating constant of 1.0-3.0. It is preferable that the photosensitive layer contains the saponine in an amount of 0.005-1.0 g/m<2> per one side of a film, and the dextrain is added to a layer farthest apart from the support and/or the photosensitive layer in an amount of 0.05-2.0 g/m<2> per one side of a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical photographic light-sensitive material and a processing method therefor.

[0002]

2. Description of the Related Art In recent years, in the photographic industry, rapid processing and low replenishment have been progressing rapidly, and it is expected that such processing will continue in the future. In order to achieve these, it is required that the photosensitive material and the processing method thereof eliminate development unevenness, development failure (white spot failure), and fixing failure.

In the medical industry, processing for a total processing time of 90 seconds was the mainstream until about ten years ago, but processing for 45 seconds has appeared since then, and processing for 30 seconds has now become widespread. On the other hand, as for the replenishment amount, it was 30
It is common to process at more than 25 cc, but current rapid processing systems, such as 30-second processing and 45-second processing, process less than 25 cc per quarter film. It has become.

As the processing speed and the replenishment rate have been reduced, the developing solution and the fixing solution have been concentrated, so that the material in the developing / fixing solution or the material eluted from the photosensitive material is removed from the developing solution or the fixing solution. It has become easier to deposit on the liquid surface.

[0005] When these deposits adhere to the photosensitive material, uneven development, poor development (white spots) and poor fixing may occur, which is likely to cause a problem. (This indicates a spot-like failure that is reduced by 0.3 or more with respect to the part.)

As a photosensitive material, in order to improve such failures in development and fixing, a binder such as gelatin is made thinner, and silver halide grains are made into tabular grains.
It is effective to design the silver content as low as possible and to increase the developing / fixing speed.

However, thinning of the binder and flattening of the silver halide grains remarkably deteriorate the resistance to scratching of the photosensitive material.

In particular, a photosensitive material for medical use has a thickness of 170
In many cases, a transparent support having a thickness of up to 180 [mu] m is used, and the feature is that the support is thicker than a color negative photosensitive material or the like. In roller transport systems for medical equipment and automatic developing machines, thicker supports are more susceptible to pressure blackening failures such as blackening of scratches, and especially in the case of double-sided photosensitive materials, there is an opportunity to come into contact with the transport system. Because of the increase, failures are more likely to occur.

Therefore, it is necessary to use a photosensitive material which does not deteriorate the pressure blackening failure performance and hardly causes uneven development.

On the other hand, conventionally, in a method of developing a photosensitive material for medical use, a pH stabilizer,
Boric acid is often contained for various purposes such as chelating agents and antioxidants.

However, if a sufficient amount of boric acid is added to achieve these objects in rapid and low replenishment processing, development unevenness and fixing failure are likely to occur, which is not preferable.

[0012]

SUMMARY OF THE INVENTION A photographic light-sensitive material and a processing method which do not cause unevenness of development, poor development, and poor fixing in rapid and low replenishment processing without deteriorating pressure resistance (scratch resistance blackening performance) are provided. .

[0013]

Means for Solving the Problems The present inventor has repeatedly studied medical photographic light-sensitive materials and processing methods for solving these problems, and has obtained the effects of the present invention by adopting the constitution of the present invention. Was found to be able to.

(1) In a photographic material having a hydrophilic colloid layer including at least one photosensitive layer on both surfaces of a transparent support, the hydrophilic colloid layer contains saponin and dextran. A medical photographic light-sensitive material characterized by the following.

(2) In a method for processing a photographic material in which a hydrophilic colloid layer including at least one photosensitive layer is provided on a transparent support, the photographic material contains saponin and dextran. The developer and the fixer in the processing method do not contain boric acid and contain at least one compound having a chelate constant of 1.0 to 3.0 with Ca.
A method for processing a medical photographic light-sensitive material, characterized by containing a seed.

(3) In the processing method for developing a photographic light-sensitive material using a developing solution and a fixing solution, the developing solution and the fixing solution do not contain boric acid and have a chelate constant of 1.0 with Ca. A method for processing a photographic light-sensitive material for medical use, wherein the developer contains at least one compound of the formula (1) to (3.0), and the developer contains saponin.

A photographic material in which a hydrophilic colloid layer including at least one photosensitive layer is provided on both surfaces of a transparent support is a so-called double-sided photosensitive material, and the transparent support is usually made of PET (polyethylene). Terephthalate) or PE
160-2 using N (polyethylene naphthalate)
It is a film base having a thickness of about 00 μm.

The saponin used in the present invention is a steroid or triterpene glycoside distributed in the plant kingdom.
It is a known compound that has long been known as a coating aid or wetting agent in the photographic industry. The type of saponin used in the present invention can be used without any particular limitation, but preferably includes saponins extracted from the roots of Queraria, and these can be easily obtained as commercial products.

The added layer of saponin in the present invention is preferably a photosensitive layer, and the added amount is 0.000 per one side of the film.
5 to 1.0 g / m ² , further 0.01 to 0.1 g / m ²
Is preferred.

Dextran is a polymer of α-1,6-linked D-glucose and is generally obtained by culturing a dextran-producing bacterium in the presence of a saccharide, but is not limited to dextran such as leuconostoc and mezenteroides. Dextran sucrase isolated from the culture of the producing bacterium can be obtained by reacting with saccharides. In addition, these native dextrans are reduced to a desired molecular weight by a partial decomposition polymerization method using an acid or an alkaline enzyme,
Those having an intrinsic viscosity in the range of 0.03 to 2.5 can also be obtained.

The dextran-modified product includes dextran sulfate, carboxyalkyldextran,
Hydroxyalkyl dextran and the like can be mentioned.
The molecular weight of these natural water-soluble polymers is 100 to 10
000 is preferred, and particularly preferably 2,000 to
50,000.

Methods for producing these dextrans and their derivatives are described in JP-B-35-11989, US Pat. No. 3,762,924, JP-B-45-12820, JP-B-45-18418, and JP-A-45-40149. Id 46-
No. 31192.

The added layer of dextran is preferably a layer furthest from the support and / or a photosensitive layer, and the amount of dextran added is 0.05 to 2.0 g / m ² , more preferably 0.1 to 0 g / m ² per one surface of the film. 0.7 g / m ² is preferred.

The saponin- and dextran-containing light-sensitive material is preferably prepared from a boric acid-free developer or fixer, or a tablet for preparing a concentrate for preparing these solutions.

The term "borate-free" means that it is not substantially contained, and the content thereof is 0.04 mol / l or less, preferably it is not contained at all.

The chelate constant with Ca is as follows.
It is the logarithm of the formation constant in which one chelating agent binds to one, measured at a temperature of 20 ° C. and an ionic strength of 0.2. The chelate constant of Ca of the present invention is 0.8 to 0.8.
It is 4.0, preferably 1.0 to 3.0, particularly 1.0 to 1.5.

Specific compounds are shown below, but are not limited thereto.

Oxalic acid, maleic acid, citraconic acid, itaconic acid, glycine, citric acid, gluconic acid, glyceric acid, glucoheptanoic acid, glycolic acid, malic acid, tartaric acid and derivatives or salts thereof, among which tartaric acid, Malic acid, gluconic acid, glyceric acid and glucoheptanoic acid and their salts are preferred.

The addition amount is 5 × 10 ^-2 to 1 × 10 ^-5 mol /
m ² (0.005 to 0.2 mol / l for a processing solution), preferably 5 × 10 ^{−2 to} 5 × 10 ⁻⁴ mol / m.
² (0.005 to 0.1 mol / l). These compounds may be used alone or in combination of two or more.

When a saponin-containing developer is used, the amount of saponin added is preferably 0.01 to 10 g / l, more preferably 0.1 to 1.0 g / l.

The medical photographic light-sensitive material of the present invention is a light-sensitive material provided with at least a hydrophilic colloid layer on a support on which an undercoat layer is coated. It is preferable that the photosensitive material is provided with two or three hydrophilic colloid layers. Here, the hydrophilic colloid layer in the present invention includes a photosensitive or non-photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, a dye layer, an undercoat layer (not an undercoat layer), and the like.

In the light-sensitive material of the present invention, a non-light-sensitive hydrophilic colloid layer can be provided between the support and the emulsion layer, and the undercoat layer can contain a polymer latex or a filter dye. .

The light-sensitive material of the present invention has a gelatin content in the hydrophilic colloid layer of 1.0 to 2.2 g / m ² per one side. More preferably, the content is 1.5 to 2.0 g / m ² , and if it is less than this, a problem may occur in abrasion resistance.

The silver halide grains used in the light-sensitive material of the present invention include silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide and the like. Can be. The silver iodide content is preferably not more than 1.0 mol% as an average silver iodide content in the whole silver halide grains.

The silver halide grains of the light-sensitive material of the present invention are:
The particles have an average aspect ratio of 3 to 15, and more preferably 3.5 to 8.0.

Tabular silver halide grains can be prepared, for example, by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodine ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution. The tabular silver halide grains used in the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is preferably from 0.2 mol% to 0.5 mol% with respect to the silver amount, and the conversion may be performed during physical ripening or after completion of physical ripening.

Silver halide grains are formed during the formation and / or growth of the grains by cadmium salts, zinc salts,
Lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), ruthenium salts (including complex salts),
It is preferable to add a metal ion using at least one selected from an osmium salt (including a complex salt) and an iron salt (including a complex salt), and to include these metal elements inside the particle and / or on the surface of the particle.

In the present invention, it is preferable to add a silver halide solvent before the desalting step in order to accelerate the developing speed. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is used in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol or more per mol of silver.
It is preferable to add ^-2 mol or less.

In the present invention, gelatin is preferably used as a dispersion medium for the protective colloid of silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low-molecular-weight gelatin (molecular weight: 20,000 to 10)
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (hereinafter abbreviated as RD), Vol. 17643 (December 1978
Month). As for the amount of gelatin, the amount of gelatin in the entire hydrophilic colloid layer per one surface of the photosensitive material is 1.0 to 2.5 g / m ² .

In the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be kept contained. When removing the salts, see RD Vol. It can be carried out based on the method described in 17643, Section II.

The silver halide grains of the present invention can be subjected to chemical sensitization. The conditions of the process of chemical ripening or chemical sensitization,
For example, the pH, pAg, temperature, time and the like are not particularly limited, and the reaction can be performed under conditions generally performed in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, using a reducing substance A reduction sensitization method, gold or a noble metal sensitization method using a noble metal or the like can be used alone or in combination. Among them, a selenium sensitization method, a tellurium sensitization method, a reduction sensitization method, etc. are preferably used.

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

In the light-sensitive material 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, (RD) 17643 and 18716 (1
November 997) and 308119 (January 1989)
(February). The types and locations of the compounds described in these three (RD) are described below.

[0045]

[Table 1]

As the support used in the light-sensitive material of the present invention, those described in the above RD can be mentioned. Suitable supports include polyethylene terephthalate film or polyethylene naphthalate film as described above. The surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like. Then, the constituent layer according to the present invention can be applied to both surfaces of the support thus treated.

In the light-sensitive material of the present invention, a silver halide emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method, or the like can be used. For details, see (RD) 17643, p. The method described in the section "Coating procedures" of 27-28 can be used.

The processing of the light-sensitive material of the present invention is carried out, for example, in the manner described in RD-17643, pages XX to XXI, pp. 29 to 30 or 3 above.
Treatment with a processing solution as described in 08119, XX to XXI, pp. 1011 to 1012 may be performed.

As a developer in black-and-white photographic processing, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-aminophenol), reductone Can be used alone or in combination. In the developer, a known agent such as a preservative, an alkali agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone agent, a water softener, and a dissolution aid can be used. A viscosity imparting agent may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

The silver halide photographic light-sensitive material of the present invention can perform ultra-rapid processing with a total processing time (Dry to Dry) of 10 to 45 seconds. Preferably it is in the range of 10 to 30 seconds. Here, the total processing time refers to the time from when the leading end of the photosensitive material to be processed is immersed in the developing tank solution of the automatic developing machine until it is dried through the squeeze roller.

In the medical photographic light-sensitive material of the present invention, the replenishment amount of the developing solution and the fixing solution is 35 to 400 ml per m ^{2 of the} light-sensitive material.
Can be processed. As a replenishment method, see
Replenishment by width and feed speed described in 5-126243,
Japanese Patent Application Laid-Open No. Sho 60-104946,
The area replenishment controlled by the number of continuously processed sheets described in -149156 may be used.

[0053]

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

Example 1 <Preparation of Seed Emulsion-1> [A1] Ossein gelatin 24.2 g Distilled water 9657 ml Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous methanol solution) 6.78 ml Potassium bromide 10 0.8 g 10% nitric acid 114 ml [B1] 2.5N AgNO ₃ aqueous solution 2825 ml [C1] Potassium bromide 841 g Finish with water to 2825 ml [D1] 1.75 N KBr aqueous solution The following silver potential control amount 42 ° C, Japanese Patent Publication No. 58-58288 58-5828
Using a mixing stirrer described in the specification of No. 9, 464.3 ml of each of the solution B1 and the solution C1 was added to the solution A1 by a simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 50 ° C. for 40 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again added. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 50 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was +
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.045 μm. It was confirmed by an electron microscope that the average particle size (circular diameter conversion) was 0.42 μm. The variation coefficient of the thickness was 42%, and the variation coefficient of the distance between twin planes was 45%.

<Preparation of Tabular Silver Bromide Emulsion> A tabular pure silver bromide emulsion was prepared using Seed Emulsion-1 and the following three kinds of solutions.

[A2] Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous methanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3669 ml with water [B2] Odor 1747g Potassium iodide Finished to 3669ml with water [C2] 2493g silver nitrate Finished to 4193ml with water While maintaining solution A2 at 50 ° C in a reaction vessel, stir vigorously and simultaneously mix the total amount of solution B2 and solution C2 over 100 minutes It was added by the method. During this time, the pH was kept at 9.0 with the KOH solution, and the pAg was kept at 8.6 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed functionally with respect to time so as to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and that they did not become multicomponent due to Ostwald ripening.

After completion of the addition, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% (by weight) of modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added as an aggregating polymer. Stir for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid is added to adjust the pH of the emulsion.
Was adjusted to 4.6 and stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.
1.25 l was added, and after stirring and standing, the supernatant was drained.

Subsequently, an aqueous gelatin solution and sodium carbonate 1
A 0% (by weight) aqueous solution was added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, it was found that the average grain size was 0.84 μm, the average thickness was 0.16 μm, the average aspect ratio was about 5.3, and the grain size distribution was 20%. Tabular silver halide grains were obtained. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide.

After the emulsion prepared above was heated to 55 ° C., the following spectral sensitizing dye (A) 450 per mole of silver halide was used.
mg, and 45 mg of the spectral sensitizing dye (B).
100 mg of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. After 10 minutes, 3.5 mg of chloroauric acid, 10 mg of sodium thiosulfate,
100 mg of ammonium thiocyanate was added. After a further 40 minutes, 0.3 mol of the following silver iodide fine grains were added. After a further 10 minutes, 5 mg of triphenylphosphine selenide was added.
Methyl-1,3,3a, 7-tetrazaindene 500m
g, and after 5 minutes, 13 g of trimethylolpropane,
After adding 30 g of gelatin, the emulsion was rapidly cooled and the emulsion was gelled to complete the chemical sensitization.

<Preparation of Silver Iodide Fine Particles> [A3] Ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water [B3] AgNO ₃ 360 g Make up to 605 ml with distilled water [C3] KI 352 g Make up to 605 ml with distilled water Solution A3 was added to the reaction vessel, and solution B3 and solution C3 were added at a constant rate over 30 minutes by a simultaneous mixing method while stirring at 40 ° C. The pAg during the addition is the normal pAg
It was kept at 13.5 by control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm. This emulsion is called a silver iodide fine grain emulsion.

(Spectral sensitizing dye) Sensitizing dye (A): 5,5'-di-chloro-9-ethyl-
Anhydride of sodium 3,3'-di- (3-sulfopropyl) oxacarbocyanine Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3 Anhydrous sodium salt of '-di- (4-sulfobutyl) benzimidazolocarbocyanine <Preparation of Subbed Support> Both sides of polyethylene terephthalate (PET) base having a thickness of 175 μm and a blue coloration of 0.17 in concentration After a corona discharge treatment of 8 Wmin / m ² , the following undercoating lower layer was applied,
For 1 minute. Then, after performing the same corona discharge treatment again, the following undercoating upper layer coating solution was applied,
Drying at 1 ° C. for 1 minute gave a subbed support.

(Undercoat Lower Layer) Latex: St (15) EA (85) 200 mg / m ² Compound A 5.0 mg / m ² Hexamethylene-1,6-bis (ethyleneurea) 5.0 mg / m ² SnO ₂ (Solid content) 300 mg / m ² (undercoating upper layer) n-butyl acrylate (10), t-butyl acrylate (35), styrene (25), hydroxyethyl methacrylate (30) 10 mg / m ² Compound L-1 30 mg / m ² Compound A 5.0 mg / m ² Acetic acid 2.0 mg / m ² Silica having an average particle size of 3 μm 3.0 mg / m ² Compound S 5.0 mg / m ²

[0066]

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<Preparation of Photosensitive Material> Three layers were simultaneously coated on both surfaces of the undercoated support obtained above, from the side closer to the support (intermediate layer 1) to the first layer. The following coating amount is an attached amount per one side.

(First layer: Intermediate layer 1) Lime-treated inert gelatin 0.2 g / m ² Filter dye F (solid dispersion) 30 mg / m ² Sodium-i-amyl-n-decyl sulfosuccinate 2.5 mg / m ² Polymer latex (glass transition point: 40 ° C.) 70 mg / m ² (second layer: emulsion layer) The additives added to the emulsion are as follows. The amount of addition other than gelatin is indicated by the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 0.7 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl-5-mercaptotetrazole 8.5 mg Colloidal silica (Ludox AM manufactured by DuPont) 35 g Lime-treated inert gelatin: total gelatin per side Was added to the amount shown in Table 2.

T-butylcatechol 150 mg compound Z 1.7 g KBr 200 mg thallium nitrate 55 mg trimethylolpropane 6.5 g dextran (average molecular weight: described in Table 2) Saponin the amount described in Table 2 Saponin the amount described in Table 2 Compound B 150 mg polystyrene sulfonic acid Sodium (average molecular weight 300,000) 1.3 g Polymer latex (having a glass transition point of 40 ° C.) 35 g * Coating was performed so that the amount of silver per side was as shown in Table 2.

(Third Layer: Protective Layer) Next, the following was prepared and applied as a protective layer coating solution. It represents the m amounts with ² per one surface below.

Lime-treated inert gelatin 0.75 g Dextran (average molecular weight: described in Table 2) Amount shown in Table 2 Sodium-i-amyl-n-decylsulfosuccinate 18 mg Polymethyl methacrylate (mat having an area average particle size of 3.5 μm) Agent) 28 mg silicon dioxide particles (matting agent having an area average particle diameter of 1.2 μm) 14 mg (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ (curing agent) 10 mg C ₇ F ₁₅ CH ₂ (CH ₂ CH ₂ O) ₁₃ H 10 mg C ₈ F ₁₇ SO ₃ K 2 mg Activator S 13 mg Hardener H 135 mg Preservative 0.1 g

[0073]

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[0074]

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The following characteristics were evaluated for the obtained sample.

<Evaluation of Scratch> Two pieces of the obtained raw samples were prepared, cut into 30 cm pieces, and then cut at 23 ° C. and RH 60% for 3 hours.
Conditioned for hours. This sample is superimposed and 50
A weight of 0 g was placed, the other hand was held by hand, and only the upper film was pulled horizontally at a speed of 5 seconds / m. After repeating this operation twice, developing treatment is performed without exposure.
The obtained sample was visually evaluated based on the following criteria. The larger the value, the better the abrasion resistance.

[0077] 4. 2. There is almost no abrasion (rubbing fog). Scratches (rub-like fog) are present, but acceptable for practical use. Many scratches (rubbing fog) make it impractical. Very many scratches (rubbing fog) <Samples for evaluating uneven development, poor development, and poor fixing> A raw sample was exposed so as to have a density of 1.0 ± 0.1. The sample was processed in terms of area equivalent to 20 pieces of four slices. The obtained treated sample was visually observed in five stages,
Developing unevenness, poor developing, and poor fixing were evaluated.

[Development Unevenness] The state of scale-like shading unevenness (density difference within 0.2), which occurred in the entire sample, was observed.

[0079] 5. 3. Very good, no development unevenness Very slight development unevenness, but good There is uneven development, but practically acceptable level. Unusable due to uneven development. The development unevenness is very strong, and the whole area is generated. [Defective development] A spot defect in the form of white spots whose density is reduced by 0.3 or more with respect to the normal part was observed.

[0080] 5. 2. There is no development defect at all, very good. 4. Observation with a 10 × loupe allows slight development defect to be confirmed. There is poor development, but practically acceptable level. Practical failure due to poor development 1. [Defective fixing] where the development failure was very strong and the entire surface was [fixing failure]. The remaining state of the spot-like silver halide emulsion layer was observed.

[0081] 5. 2. There is no fixing defect at all, very good. 4. Observation with a 10 × magnifier allows slight fixing defects to be confirmed. 1. There is fixing failure, but practically acceptable level. Improper fixing, impractical <Fixing process> For the developing process, the automatic developing machine SRX-502 (manufactured by Konica Corporation) was modified to increase the line speed to 1.8 times. Using prescription developer and fixer
Processing was performed for 25 seconds with ryto Dry. The amount of replenishment for development and fixing is 4 sheets (25.4cm x 30.5cm) per sheet.
It was set to be 10 cc. In addition to the following developing / fixing solution formulation, boric acid or tartaric acid, malic acid, gluconic acid, and citric acid were added as shown in Table 3 to prepare a processing solution for evaluation.

(Developer Formulation) Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraaminepentaacetic acid 120 g Sodium hydrogen carbonate 132 g 5-methylbenzotriazole 1.2 g 1- Phenyl-5-mercaptotetrazole 0.2 g 1,4-dihydroxybenzene 340 g Add water to make 5000 ml. Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitro Indazole 0.4g Starter solution formulation (for 1 liter finishing) Glacial acetic acid 120g Potassium bromide 225g Add water to make up to 1000ml (Fixing solution formulation) Part-A (for 18 liter finishing) Thio Ammonium sulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B (for finishing 18 liter) Sulfuric acid Aluminum 800g (Preparation of developer) The developer is prepared by adding P
Art-A and Part-B were added simultaneously, and while stirring and dissolving, 0.05 mol / l (3.1 g / l) boric acid and water were added to make up to 12 liters, and the pH was adjusted to 10.40 with glacial acetic acid. And used as a developer.

20 ml of a starter solution was added per liter of the developer, and the pH was adjusted to 10.40 to obtain a working solution.

(Preparation of Fixing Solution) The fixing solution was prepared by simultaneously adding Part-A and Part-B to about 5 liters of water, adding water while stirring and dissolving, and adding 0.05 mol / l of boric acid.
(3.1 g / l), and the mixture was adjusted to 18 liters. The pH was adjusted to 4.4 with sulfuric acid and sodium hydroxide, and this was used as a fixing solution working solution and a fixing solution replenisher.

The processing temperatures were 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing and 50 ° C. for drying, respectively. Table 2 shows the obtained results.

[0086]

[Table 2]

The light-sensitive material of the present invention has good resistance to scratching and blackening, and has improved development unevenness, poor development and poor fixing in rapid and low replenishment processing.

Example 2 The photosensitive material No. 1 prepared in Example 1 was used. Using No. 1 and the developing / fixing solution, saponin was added to the developing solution according to the contents shown in Table 4. However, boric acid was not added to the developing solutions BF and fixing solutions bb, but tartaric acid, malic acid or gluconic acid was added as shown in Table 3. Otherwise, evaluation was performed in the same manner as in Example 1. Table 4 shows the results.

[0089]

[Table 3]

[0090]

[Table 4]

By the processing method of the present invention, unevenness of development, defective development, and defective fixing in rapid / low replenishment processing are improved.

[0092]

According to the present invention, there is provided a photographic light-sensitive material and a processing method that do not cause development unevenness, development failure, or fixing failure in rapid and low replenishment processing without deteriorating pressure resistance (scratch blackening resistance). be able to.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03C 5/38 G03C 5/38

Claims (3)

[Claims] 1. The method according to claim 1, wherein both sides of the transparent support have at least one
1. A medical photographic light-sensitive material provided with a hydrophilic colloid layer including a photosensitive layer, wherein the hydrophilic colloid layer contains saponin and dextran. 2. A method for processing a photographic material in which a hydrophilic colloid layer including at least one photosensitive layer is provided on a transparent support, wherein the photographic material contains saponin and dextran, A medical solution characterized in that the developing solution and the fixing solution in the processing method do not contain boric acid and contain at least one compound having a chelate constant of 1.0 to 3.0 with Ca. Processing method of photographic photosensitive material. 3. A processing method for developing a photographic photosensitive material using a developing solution and a fixing solution, wherein the developing solution and the fixing solution do not contain boric acid and have a chelate constant of 1.0 to 1.0 with Ca. 3. A method for processing a photographic light-sensitive material for medical use, comprising at least one compound of formula (3.0) and the developer containing saponin.