JPH0756255A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material which has high sensitivity, has no dependency on development processing temp. and fixing defects even for rapid processing by an automatic developing machine. CONSTITUTION:This silver halide photographic sensitive material has at least one layer of photosensitive silver halide emulsion layers and nonphotosensitive hydrophilic colloidal layers on both sides of a base. The relation of SA, SB and SB' is expressed by equations [1] SB/SB'>4.0 and [2] SA/SB=1.5 to 20 when the sensitivity of the A surface when the photosensitive material is exposed only from the surface (A surface) on one side of the base is defined as SA, the sensitivity of the surface (B surface) on the other side as SB' and the sensitivity of the B surface when the photosensitive material is exposed from only the B surface of the base as SB. Further, a polymer latex bonded with gelatin is incorporated into at least one layer of the emulsion layers and/or nonphotosensitive hydrophilic colloidal layers on respective surfaces.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity silver halide photographic light-sensitive material, and more particularly to a high-sensitivity silver halide photographic light-sensitive material having good sharpness and capable of rapid processing. is there.

[0002]

2. Description of the Related Art Conventionally, in a light-sensitive material in which light is irradiated from only one side of the light-sensitive material, it has been customary to provide a light-sensitive silver halide emulsion layer only on one surface of the light-sensitive material.
For example, CRT film and indirect X-ray film are
It is generally a so-called single-sided light-sensitive material having a photosensitive silver halide emulsion layer on only one side of the film.

Among direct X-ray photography films, mammography photography films and the like having a photosensitive silver halide emulsion layer on only one side are used.

These single-sided light-sensitive materials are highly sharp because they are not affected by crossover light, as compared with so-called double-sided light-sensitive materials having a photosensitive silver halide emulsion layer on both sides of a support.

However, in order to increase the sensitivity of the above single-sided light-sensitive material, a large amount of light-sensitive silver halide is provided on one side as compared with a double-sided light-sensitive material (for example, double-sided light-sensitive material for direct X-ray photography). I had no choice but to apply the emulsion.

However, when many silver halide emulsions are attached to one side of the support, problems arise in processing. For example, when rapid processing is performed using an automatic processor, defective fixing and the like often occur.

The present applicant has solved the above problems by using a double-sided coating silver halide photographic light-sensitive material in which the emulsions on the A side and the B side have different sensitivities in JP-A-3-260641. The inventor has invented a technique which has high sensitivity and has no problem even when rapid processing is performed, and which also satisfies the requirement of high sharpness.

However, in the present method, since silver halide emulsions having different compositions are used on both sides, there is a problem that the characteristic curve obtained is easily affected by the temperature variation of the developing solution.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to improve the temperature dependence of development processing even for rapid processing by an automatic processor.
Another object of the present invention is to provide a high-sensitivity medical silver halide photographic light-sensitive material which is free from fixing defects. Other purposes will be apparent from the following description.

[0010]

The above object of the present invention is to provide a silver halide copying light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on both sides of a support. , The sensitivity of surface A when exposed from only one surface of the support (hereinafter appropriately referred to as “A surface”) is SA, and the sensitivity of the other surface is hereinafter referred to as “B surface” as appropriate. If the sensitivity is SB ′ and the sensitivity of the B side when exposure is performed only from the B side of the support is SB, the above S
The relationship between A, SB, and SB 'is expressed by the following formulas [1] and [2].
And a polymer latex bound to gelatin in at least one of the emulsion layer and / or the non-photosensitive hydrophilic colloid layer on each side.

Formula [1] SB / SB '> 4.0 Formula [2] SA / SB = 1.5-20.

In the present invention, the value of SB / SB 'exceeds 4.0 as shown in the formula [1], and this value is preferably 4.5 or more, more preferably 5.0 or more.

In the present invention, the value of SA / SB is 1.5 to 20 as shown in the formula [2], but this value is preferably in the range of 2.5 to 10.

The silver halide grains used in the photosensitive silver halide emulsion layer for constituting the light-sensitive material of the present invention are not particularly limited and are arbitrary.

That is, as the silver halide, any of silver bromide, silver iodobromide, silver chlorobromide, silver chloride and the like used in ordinary silver halide emulsions can be appropriately used. Silver iodobromide is preferably used. The crystal habit and grain size of the silver halide grains are not limited and are arbitrary.

The silver halide emulsion used may be spectrally sensitized. For example, ortho sensitization, panchromatic sensitization, and infrared spectral sensitization can be performed.

As the silver halide photographic emulsion, any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used. Even if each is independent, several kinds thereof are mixed. Although it may be used, a monodisperse emulsion is preferably used.

As the hydrophilic colloid in the present invention,
Examples thereof include hydrophilic colloids used for photography such as gelatin, albumin, polysaccharides, cellulose derivatives, polyvinyl compounds including polyvinyl alcohol derivatives, and acrylamide polymers.

Next, the polymer latex combined with gelatin used in the present invention (hereinafter referred to as gelatin latex) will be described.

Ordinary latex is dispersed in water by a surfactant, but gelatin latex which can be used in the present invention is characterized in that it is dispersed and stabilized by gelatin to which polymer latex is bound. In this case, the polymer and gelatin may be directly bonded or may be bonded via a crosslinking agent. Therefore, the monomers constituting the latex include carboxyl group, amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, ester group, methylol group, cyano group, acetyl group, unsaturated carbon bond. It is desirable to include those having a reactive group such as.
When a cross-linking agent is used, it is possible to use one that has been used as a usual cross-linking agent for gelatin. For example, aldehyde-based, glycol-based, triazine-based, epoxy-based, vinyl sulfone-based, oxazoline-based, methacrylic-based, acrylic-based, etc. crosslinking agents can be used.

The preferred gelatin latex according to the invention is characterized in that at least part of the polymerization reaction of the polymer is carried out in a solvent containing at least gelatin. The weight ratio of gelatin and polymer at the time of synthesis (finally obtained as latex) was Gel / Poly = 1/10.
0 to 2/1 is preferable, and 1/50 to 1/2 is particularly preferable.

Further, in the present invention, the particle size of the latex is preferably 0.3 μm or less. Particularly preferred particle size is 0.01-
It is 0.27 μm.

The composition of the monomer of the polymer latex contained in the photographic light-sensitive material of the present invention includes, for example, US Pat. Nos. 2,772,166, 3,325,286 and 3,411,911.
Issue 3, Issue 3,311,912, Issue 3,525.620, RD-19551 (1980.
Examples thereof include acrylates, methacrylates, and hydrates of vinyl polymers such as styrene described in 7).

The gelatin latex used in the present invention may be contained on both sides of the support and added to at least one hydrophilic colloid layer on each side. A preferable result is obtained when it is added to the non-photosensitive hydrophilic colloid layer on the side of the hydrophilic hydrophilic colloid layer. A conventionally known latex may be added to the layer to which the gelatin latex of the present invention is added and / or not added. When included on both sides of the support, the type and / or amount of polymer latex included on each side may be the same or different. As the latex component of the gelatin latex used in the present invention, compounds L-1 to L-26 shown in Japanese Patent Application No. 4-97922 can be preferably used. Specific examples of the latex used in the present invention are shown below. Needless to say, the constituent components (not only the composition ratio) of the latex used here are not limited to these specific examples.

[0025]

[Chemical 1]

[0026]

[Chemical 2]

[0027]

[Chemical 3]

As the transparent support of the double-sided light-sensitive material of the present invention, any transparent support may be used as long as it is capable of exposing the light-sensitive side and the opposite side of the photosensitive emulsion layer. You can All general transparent supports for photographs can be used.For example, a film made of a semi-synthetic product such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate, or a synthetic polymer can be used. Can be used. The support may be colored with a dye or pigment.

In general, the surface of these supports may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may contain various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include (RD) No. 1 described above.
Various compounds described in 7643, (RD) No. 18716 and (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 ~ 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 ~ 5 X Surfactant 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogenation of the Invention Examples of the support used for the silver photographic light-sensitive material include those described in RD above,
A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or subjected to corona discharge or ultraviolet irradiation.

The photographic processing of the light-sensitive material of the present invention is carried out, for example, by RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to XX.
I, pp. 1011-1012, treatment with a treatment solution may be performed. This process may be either a monochrome photographic process for forming a silver image or a color photographic process for forming a dye image. The treatment temperature is usually in the range of 18 ° C to 50 ° C.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. For the developer, known agents such as preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants,
A defoaming agent, a toning agent, a water softening agent, a dissolution aid, a viscosity imparting agent and the like may be used as necessary.

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

[0035]

【Example】

Example 1 An example of the present invention will be described below. Naturally, the present invention is not limited to the examples described below.

(Synthesis of Comparative Latex A) Water 401 containing sodium dodecylbenzenesulfonate (O.Olkg) and ammonium persulfate (0.05 kg) was added to a solution (a) styrene under a nitrogen atmosphere while stirring at a liquid temperature of 60 ° C. 3.0 kg, (a) methyl methacrylate 3.0 kg, and (u) ethyl acrylate 3.2 kg mixed solution and (d) 2-acrylamido-2-
0.8 kg of sodium salt of methylpropanesulfonic acid was added over 1 hour, then stirred for 1.5 hours, steam distilled for 1 hour to remove residual monomer, and cooled to room temperature, and then sodium hydroxide was used for pH. Was adjusted to 6.0.

The latex solution obtained was made up to 55 kg with water. As described above, a monodisperse latex having an average particle size of 0.11 μm was obtained.

(Synthesis of gelatin latex L-5) Water 60
1 kg of gelatin, 1.0 kg of sodium dodecylbenzene sulfonate, and 0.05 kg of ammonium persulfate were added to a liquid with stirring at a liquid temperature of 60 ° C. under a nitrogen atmosphere (a) styrene 3.0 kg, (a) methyl methacrylate A mixture of 3.0 kg and (U) ethyl acrylate (3.2 kg) and sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (0.8 kg) were added over 1 hour, and then the mixture was stirred for 1.5 hours and then steam-distilled for 1 hour to remain. After removing the monomer, the mixture was cooled to room temperature, and then the pH was adjusted to 6.0 with ammonia.

The latex solution obtained was made up to 75 kg with water. As described above, a monodisperse latex having an average particle size of 0.1 μm was obtained.

(Preparation of Sample) Monodispersed silver iodobromide grains containing 2.0 mol% of silver iodide having an average grain size of 0.2 μm are used as nuclei.
Silver iodobromide containing 30 mol% of silver iodide has a pH of 9.3 and a pH of 7.5.
And then added equimolar amounts of potassium bromide and silver nitrate at pH 7.8 and pH 8.9 to obtain silver iodobromide grains having an average silver iodide content of 2.3 mol. ), 0.
Three types of monodisperse emulsion particles of 70 μm (a) and 0.41 μm (c) were prepared. The emulsion was desalted from excess salts by the usual flocculation method. That is, the temperature was maintained at 40 ° C., and a formalin condensate of sodium naphthalenesulfonate and an aqueous solution of magnesium sulfate were added to cause aggregation. After removing the supernatant liquid, pure water at 40 ° C. was further added, and an aqueous magnesium sulfate solution was added again to cause coagulation to remove the supernatant liquid. Spectral sensitizing dye 5,5 for each
Anhydrous sodium'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine and spectral sensitizing dye 5,5'-di- (butoxycarbonyl) -1,1 ' -Diethyl-
Anhydrous 3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt in a weight ratio of 200: 1,
After adding the total amount to 800 mg per 1 mol of silver halide, ammonium thiocyanate salt was chemically ripened by adding 2.4 × 10 ^-3 mol per 1 mol of silver and an optimum amount of chloroauric acid and hypo. Then 4-hydroxy-6-
Methyl-1,2,3,7 tetrazaindene (2 × 10 ^-2 mol) was added for stabilization.

Using the thus obtained three kinds of emulsions (a, b and c), the following emulsion additives and the amounts of comparative latex A and gelatin latex L-5 shown in Table 1 were added, and the following emulsion coating solution was prepared. Prepared. Each number indicates a mixing ratio.

Coating Solution 1 Emulsion A: Emulsion A: Emulsion C = 2
0.0: 40.0: 40.0 Coating liquid 2 Emulsion A: Emulsion A = 33.3: 66.7 Coating liquid 3 Emulsion C only Coating liquid 4 Emulsion A: Emulsion A = 40.0: 60.0 Coating liquid 5 Emulsion A: Emulsion A = 20.0: 80.0 Coating liquid 6 Emulsion A only The additives used for the ripened emulsion are as follows. The addition amount is indicated by the amount per mol of silver halide.

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-dihydroxybenzene-4- Ammonium sulfonate 4g 2-Mercaptobenzimidazole sodium 5-sulfonate 1.5mg

[0044]

[Chemical 4]

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g Next, the following was prepared as a protective layer coating liquid. The additive is shown in the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size) Matte agent of 1.2 μm) 0.5 g Ludox AM (DuPont) (colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg Glioxal 40% aqueous solution (hardener) 1.5 ml

[0047]

[Chemical 5]

Along with the above additives, the amounts of comparative latex A and gelatin latex L-5 shown in Table 1 were added,
A protective film coating solution was prepared.

The emulsion layer coating solution and the protective layer coating solution thus obtained were coated on a polyethylene terephthalate support which had been subbed, and two slide hopper type coaters having a construction shown in Table 1 were used to form a coating solution of 90 m / min. Both sides were simultaneously coated on the support at a speed and dried for 2 minutes and 15 seconds to obtain a sample.

The coated samples Nos. 1 to 16 thus obtained were evaluated as follows. Sensitometric evaluation was performed.

<Evaluation of Finishing Sensitivity> X was added to the obtained sample.
Adhere X-ray intensifying screen KO-250 on the A side and after X-ray irradiation through penetrometer B type, use SRX-501 automatic processor XD-
Processing was performed for 45 seconds at 35 ° C. with SR developing solution. (Both are manufactured by Konica Corp.) The sensitivity of each sample developed as described above was evaluated. The sensitivity was shown as a relative value with the reciprocal of the exposure energy amount required for giving the density of fog 1.0 of Sample No. 1 being 100. The results are shown in Table 2.

<Method of measuring SA, SB, SB '> SA, SB, S of the silver halide photographic light-sensitive material of the present invention
The B'sensitivity means the value obtained by the following method.

Exposure condition Fluorescent intensifying screen (KO-250) (Konica Corporation) X-ray irradiation condition Tube voltage: 70Kvp Grid: Not used Tube current: 100mA Time: 100msec Distance: 1.85m Exposure method Cassette The intensifying screen is placed only on the back side of, and the sample (film) is placed on the intensifying screen, and then exposure is performed under the above X-ray irradiation conditions through the aluminum steps.

Current image Developer: XD-90 (manufactured by Konica Corporation) Development temperature: 35 ° C. Fixer: XF (same as above) Fixing temperature: 33 ° C. Developer: XF-500 (same as above) Sensitivity measurement method Development Regarding the latter sample, first, the sample exposed only from the A surface is divided into two, one surface is removed from the B surface for SA measurement, and the other is removed from the A surface for SB ′ measurement. Next, for the sample exposed only from the B surface, the A surface is similarly removed for SB measurement. A characteristic curve is obtained for each of the three types of samples obtained, and the reciprocal of the exposure amount required to obtain the density of base density + fog density + 1.0 is obtained from the obtained characteristic curve.
A, SB, SB '. Sensitivity is shown as relative sensitivity with SA of Sample No. 1 as 100.

<Fixability Test> Each sample was immersed in a fixing solution (XF-SR) at 25 ° C., and the time until the silver halide was completely eluted was measured. In this measurement, if the time until elution exceeds 8 seconds, defective fixing occurs in the treatment for 45 seconds, and the color is discolored during long-term storage.

<Treatment Temperature Dependence> Similar to the sensitivity test,
Development temperature 3 using automatic processor SRX-501, XD-SR, XF-SR
The treatment was performed at 2, 35 and 38 ° C for 45 seconds. The sensitivity and contrast of the resulting sample were measured. The contrast represents the slope of the density of 0.25 to 2.0 in the characteristic curve.

[0057]

[Table 1]

[0058]

[Table 2]

As is clear from Tables 1 and 2, the light-sensitive material of the present invention has high sensitivity, and the silver halide photographic light-sensitive material has no dependency on development processing temperature even in rapid processing by an automatic developing machine and no fixing failure. It turns out that it is a material.

[0060]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and having no dependency on development processing temperature even in rapid processing by an automatic processor and fixing failure is obtained.

Claims (1)

[Claims] 1. A silver halide photothermographic material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on both sides of a support. When the exposure is performed only from the "A side", the sensitivity of the A side is SA, the sensitivity of the other side (hereinafter appropriately referred to as "B side") is SB ', and the B of the support is B. When the sensitivity of the B side when exposed from only the side is SB, the relation of SA, SB, and SB ′ is represented by the following formulas [1] and [2], and the emulsion is A silver halide photographic light-sensitive material, characterized in that a layer and / or at least one of the non-photosensitive hydrophilic colloid layers contains a polymer latex bound to gelatin. Formula [1] SB / SB '> 4.0 Formula [2] SA / SB = 1.5 to 20