JPH08201947A - Silver halide photographic material - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a silver halide photographic light-sensitive material having high sensitivity even in rapid processing and having less residual color. In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, at least one light-sensitive silver halide emulsion layer is chlorinated. Hydrophilic, containing silver halide grains having a silver content of 50 mol% or more, and having an absorbance in the wavelength region of 200 to 400 nm of less than 1.0 in the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer. Achieved by a silver halide photographic light-sensitive material characterized by containing a polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having high sensitivity and capable of rapid processing.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials), especially medical X-ray light-sensitive materials, are required to have high sensitivity and high image quality as well as rapid processability. Since rapid processing shortens the processing time, it is necessary to have good developability and fixability.
It is known that the developability is improved by using silver chloride grains as the silver halide grains in the light-sensitive material, but silver chloride has a drawback that it has lower sensitivity than silver bromide or silver iodide.

The light-sensitive material must contain a material having the properties of both a deflocculant and a binder for preventing the fusion or agglomeration of silver halide grains. It is known that various hydrophilic colloids are useful as such materials. For example, alkali-treated gelatin or acid-treated gelatin and gelatin derivatives are preferably used.

However, since gelatin contains nitrogen and sulfur, it absorbs ultraviolet light, particularly light having a wavelength of less than 300 nm. Since silver halide has photosensitivity to a wavelength of 200 to 400 nm, absorption of light by gelatin reduces ultraviolet light reaching silver halide grains.
This causes a decrease in sensitivity, and there is a problem that there are many residual colors. Therefore, a compound that does not have the disadvantages of gelatin and has the same performance as a binder as gelatin is desired.

Japanese Unexamined Patent Publication (Kokai) No. 6-194765 discloses a method of precipitating silver halide grains by using a water-soluble starch having an absorbance of less than 1.0 in the wavelength region of 200 to 400 nm as a peptizing agent. The effective use as a silver halide photographic light-sensitive material has not been clarified, and an effective method for the above problems has not yet been found.

[0006]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity even in rapid processing and has less residual color. .

[0007]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support. At least one light-sensitive silver halide emulsion layer contains silver halide grains having a silver chloride content of 50 mol% or more, and the silver halide emulsion layer and / or the non-light-sensitive hydrophilic colloid layer has a thickness of 200 to 400 nm. The silver halide photographic light-sensitive material is characterized by containing a hydrophilic polymer having an absorbance in the wavelength region of less than 1.0.

The present invention will be described in detail below.

The hydrophilic polymer used in the present invention has a property as a peptizing agent and / or a binder, and has been conventionally used.
It is a compound that can be exchanged with a part or the whole amount of gelatin used, and is 1.0 in the wavelength range of 200 to 400 nm.
It should have an absorbance of less than. The absorbance in the present invention is obtained by passing a solution having a concentration of 2 g / l through a transmission path having a thickness of 1 cm.
It is represented by a value when measured by continuously changing light having a wavelength of 200 to 400 nm.

Examples of the hydrophilic polymer used in the present invention include polysaccharides such as starch, cellulose, dextrin and dextran, and derivatives thereof. Water-soluble starch, particularly potato starch, is preferably used. Potato starch is preferred because it is easily available and inexpensive. In the present invention, these hydrophilic polymers may be used as a deflocculant during the preparation of silver halide grains, or as a binder when coating an emulsion.

The silver halide grains of the silver halide emulsion layer according to the present invention are normal crystal grains, that is, all isotropically grown grains such as cubes, octahedrons and tetrahedrons, or polyhedral grains such as spheres. Although it may be a conventional crystal type, a twin crystal having a plane defect, or a mixed type or a complex type thereof, tabular silver halide grains are preferably used.

The tabular silver halide emulsion according to the present invention comprises
The average value of particle diameter / thickness (called aspect ratio) (called average aspect ratio) is 3 or more, preferably 3 to
20 and particularly preferably 3-10.

In the light-sensitive silver halide emulsion used in the present invention, 50% or more, more preferably 70% or more of the total projected area of silver chloride, silver chloride, silver chlorobromide or chloroiodo has a silver chloride content of 50 mol% or more. It is preferably composed of silver halide or silver chloroiodobromide.

The crystal structure of silver halide may be a uniform composition or a core / shell structure composed of a silver halide composition having different internal and external parts.

The average silver iodide content and the average silver chloride content of the silver halide emulsion according to the present invention are controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide and chloride. be able to.
If necessary, a silver halide solvent such as ammonia, thioether, thiourea or the like can be used during the production of silver halide grains.

For the emulsion, a water washing method such as a Noudel water washing method or a flocculation sedimentation method is used to remove soluble salts. A preferred washing method is, for example, Japanese Examined Patent Publication No. 35-160.
Particularly preferable desalting method is a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-A No. 86 or a method using G3, G8, etc., as an aggregation polymer agent described in JP-A-63-158644. .

The chemical ripening temperature of the emulsion according to the present invention is arbitrarily determined, but is preferably in the range of 20 to 90 ° C, particularly preferably 30 to 80 ° C, and further preferably 35 to 70 ° C.

The emulsion according to the present invention may be selenium-sensitized with a selenium compound.

As the selenium sensitizer used in the present invention, a conventionally known selenium compound can be used. The selenium sensitization is usually carried out by adding an unstable selenium compound and / or a non-unstable selenium compound to a silver halide emulsion and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Examples of unstable selenium compounds include Japanese Patent Publication No. 44
It is preferable to use the compounds described in JP-B-15748 and JP-B-43-13489. Specific examples of unstable selenium compounds include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg, 2-selenopropionic acid). , 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides,
Examples include colloidal metal selenium.

As the non-labile selenium compound used in the present invention, for example, the compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds are selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinedione and derivatives thereof.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added at the time of chemical sensitization, preferably before the start of chemical sensitization.

The silver halide emulsion of the present invention is spectrally sensitized with a sensitizing dye. As the sensitizing dye that can be used in the present invention,
Cyanine, merocyanine or complex cyanine,
Any of commonly used sensitizing dyes such as complex merocyanine, styryl and hemicyanine may be used.

Examples of the sensitizing dye that can be used in the present invention include US Pat. Nos. 3,522,052 and 3,619,197,
No. 3,713,828, No. 3,615,643, No. 3,615,632, No. 3,6
17,293, 3,628,964, 3,703,377, 3,666,48
No. 0, 3,667,960, 3,679,428, 3,672,897,
No. 3,769,026, No. 3,769,026, No. 3,556,800, No. 3,6
15,613, 3,615,635, 3,615,638, 3,705,80
No. 9, No. 3,632,349, No. 3,677,65, No. 3,770,440,
3,770,449, 3,769,025, 3,745,014, 3,7
No. 13,828, No. 3,567,458, No. 3,625,698, No. 2,526,63
2, 2,503,776, JP-A-48-76525, Belgian patent
Examples thereof include those described in the specification such as 691,807.

The addition amount of the sensitizing dye is not uniform depending on the kind of dye, the purpose of spectral sensitization or the emulsion composition, but is in the range of 1 × 10 ^-4 mol to 1 × 10 ^-3 mol per mol of silver halide. Well, preferably 2 × 10 ⁻⁴ mol to 8 × 10 ⁻⁴ mol. The sensitizing dye may be added at any time after the growth step of the parent grain and before the chemical sensitization step. The dye can be added by being dissolved in a hydrophilic solvent such as methanol or ethanol, or dispersed in water as a solid.

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 that can be used in such a step include Research Disclosure (RD) 17643, (RD) 18716 (November 1979) and
Various compounds described in (RD) 308119 (December 1989) can be mentioned. The types and locations of the compounds described in these three (RD) are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB 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 Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 to 4 XXII Support 28 XVII 1009 XVII Photosensitization of the present invention The above-mentioned R is used as the support used for the material.
Examples of suitable supports include plastics, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, corona discharge or ultraviolet irradiation. May be given. Then, the emulsion of the present invention can be coated on both sides of the support thus treated.

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

The processing of the silver halide photographic light-sensitive material of the present invention is described, for example, in (RD) -17643, XX to XXI, pages 29 to 30, or 308119, XX to XXI, pages 1011 to 1012. Treatment with such a treatment liquid may be performed.

As the processing agent in the black and white photographic processing agent,
Dihydroxybenzenes (eg hydroquinone),
3-Pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-aminophenol) and the like can be used alone or in combination. In addition, a known developer such as a preservative,
If necessary, an alkali agent, a pH buffering agent, an antifoggant, a hardener, a development accelerator, a surfactant, a defoaming agent, a toning agent, a water softener, a solubilizing agent, a viscosity imparting agent, etc. may be used. Good.

A fixing agent such as thiosulfate or thiocyanate is used for the fixing solution. Further, a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, preservatives, pH adjusters, water softeners, etc. may be included.

In the present invention, the total processing time (Dry to Dry)
It is possible to perform ultra-rapid treatment of 60 seconds or less, more preferably 40 seconds or less. The term "development process time" or "development time" as used in the present invention means that the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of an automatic developing machine (hereinafter, "developing machine") and then in the next fixing solution. "Fixing time" is the time from immersion in the fixing tank liquid to the next washing tank liquid (stabilizing liquid), and "Washing time" is the immersion in the washing tank liquid. Say time Further, "drying time" is usually 35 to 100 ° C, preferably 4
A drying zone in which hot air of 0 to 80 ° C is blown is installed, and the time during which the zone is in the drying zone.

In the development processing of the present invention, the development time is 15 seconds or less, preferably 10 seconds or less. The development temperature is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The fixing temperature and time are preferably 20 to 50 ° C. and 2 to 12 seconds, and more preferably 30 to 40 ° C. and 2 to 10 seconds. Washing or stabilizing bath temperature and time is 0
It is preferably 2 to 15 seconds at 50 ° C, more preferably 2 to 8 seconds at 15 to 40 ° C. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed (or stabilized) is dried through a squeeze roller that cuts out washing water. Drying is performed at 40 to 100 ° C, and the drying time can be appropriately changed depending on the environmental temperature.
It is usually 3 seconds to 12 seconds, particularly preferably 3 at 40 to 80 ° C.
~ 8 seconds, preferably using a far infrared heater.

In the light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be coated on the support by various coating methods. Slide hopper coating method, curtain coating method, extrusion coating method, etc.
For details, see Research Disclosure 176 (Research D
The method described in the section "Coating Procedure" on pages 27 to 28 can be used.

In addition, various known photographic techniques can be used in the practice of the present invention.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples. Needless to say, the present invention is not limited to the examples described below.

Example 1 (Preparation of silver chloride emulsion) Preparation of EM-1 (pure silver chloride tabular grains) <Solution A> High methionine gelatin (containing 9.7 mM methionine per 1 g gelatin) 90 g CaCl ₂ .H ₂ O 440 g Distilled water to 6000 ml <Solution B> Silver nitrate 1017 g Distilled water to 1800 ml At 40 ° C, the pH of solution A was adjusted to 5.1 using a mixing stirrer as shown in JP-B-58-58288 and 58-58289. Adjust to
Solution B, 29 ml, was added over 4 minutes, then the addition rate was linearly accelerated over another 55 minutes (from start to finish
9.32 times), during which the whole amount of solution B was added. Solution B
4,16,36 minutes after the start of the addition of
30 ml was added. After 10 minutes, 3.78 g of 3M CaCl ₂ solution was added. During the addition of the adenine solution and the CaCl ₂ solution, the inflow of the solution B was stopped for 1 minute, and the additives were mixed uniformly. During this period, the pH was controlled to be constant by adding NaOH or HNO ₃ . After the addition, in order to remove excess salts, desalting (destroyed by Kao Atlas) aqueous solution and magnesium sulfate aqueous solution were used for precipitation desalting, and a total of 92.2 g of ossein gelatin and / or potato potato starch (in the coated sample) The amount of gelatin and potato starch obtained in (1) was adjusted to the ratio shown in Table 1) to make 2500 ml, and the mixture was stirred and redispersed to prepare EM-1.

Approximately 3000 particles of EM-1 were observed and measured by an electron microscope and their shapes were analyzed. The average particle diameter was 2.1.
The average particle thickness was 0.23 μm, the sphere-equivalent particle size was 0.93 μm, and the coefficient of variation was 18%.

Preparation of EM-2 (silver chlorobromide AgBr _0.10 Cl _0.90 tabular grains) <Solution A> High methionine gelatin (methionine 59.7 mM per 1 g of gelatin) 103 g 4,5,6-triaminopyrimidine 343 g NaCl 246 g NaBr 48 g Distilled water to 6000 ml <Solution B> Silver nitrate 793 g Distilled water to 2000 ml At 40 ° C, the pH of solution A in the mixing stirrer shown in JP-B-58-58288 and 58-58289 is changed to 5.6 Adjust and solution B
Was added over 1 minute. Then the addition rate
Linear acceleration over 55 minutes (9.8 from start to finish)
And the total amount of Solution B was added in the meantime. Gelatin solution 411 ml was added 1, 5 and 18 minutes after the start of addition of the solution B. After 5 and 18 minutes 1371 g of 4M NaCl solution and 20 mM
Of 4,5,6-triaminopyrimidine solution of 343 g was added.
During the addition of the above materials, the silver flow was stopped for 1 minute and the additives were mixed uniformly. During this period, the pH was controlled to be constant by adding NaOH or HNO ₃ . EM-1 after addition
Precipitation desalting was carried out in the same manner as in (1), and an aqueous solution containing ossein gelatin and / or potato starch was added and the mixture was stirred and redispersed.

Approximately 3000 particles of EM-2 were observed and measured by an electron microscope and their shapes were analyzed. The average particle diameter was 1.8.
The average particle thickness was 0.12 μm, the sphere-equivalent particle size was 0.67 μm, and the coefficient of variation was 18%.

Preparation of EM-3 (silver chlorobromide AgBr _0.50 Cl _0.50 tabular grains) The procedure of EM-2 was repeated except that 192 g of NaBr was added to the mixer.

Approximately 3000 particles of EM-3 were observed and measured by an electron microscope to analyze the shape, and the average particle diameter was 2.0.
The average particle thickness was 0.13 μm, the sphere-equivalent particle size was 0.74 μm, and the coefficient of variation was 18%.

Next, the obtained emulsion was chemically sensitized by the following method.

After EM-1 to EM-3 were heated to 50 ° C., the following sensitizing dyes (A) and (B) were respectively added to 200 m per 1 mol of silver.
g and 14 mg were added, and 10 minutes after that, 60 mg of ammonium thiocyanate, 1.45 mg of chloroauric acid and 3.3 mg of sodium thiosulfate were added as chemical sensitizers for chemical ripening. After the completion of the chemical ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was stabilized with 3 × 10 ^-2 mol. Emulsions EM-1 to EM-3 were obtained.

Sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous Sensitizing dye (B): 5, 5'-dibutoxycarbonyl-1,1'-
Diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride (preparation of sample) The following various additives were added to each emulsion. The amount of addition is shown in an amount per mole of silver halide.

1-phenyl-5-mercaptotetrazole 10 mg 1-trimethylolpropane 14 g t-butyl-catechol 68 mg polyvinylpyrrolidone (molecular weight 10,000) 850 mg styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenylphosphonium chloride 50 mg 1 Ammonium 3,3-dihydroxybenzene-4-sulfonate 1.7 g 1,1-Dimethylol-1-bromo-1-nitromethane 6.2 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂
700 mg

[0046]

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The additives used in the protective layer liquid are as follows. The added amount is shown as the amount per 1 g of gelatin or starch.

Matting agent composed of polymethylmethacrylate having an average particle size of 5 μm 21 mg Matting agent composed of polymethylmethacrylate having an average particle size of 3 μm 28 mg Glyoxal
50 mg

[0049]

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The above coating solution was uniformly applied to both surfaces of a blue-colored polyethylene terephthalate film base having a thickness of 180 μm and subjected to undercoating treatment, and dried to prepare samples shown in Table 1.

The coated silver amount is 2.0 g / side.
The amounts of m ² , gelatin and potato starch were adjusted for all the samples so that the amounts were as shown in Table 1 per side.

(Evaluation of Sensitometry) The obtained sample was sandwiched between fluorescent intensifying screens for X-ray photography, KO-250 (manufactured by Konica Corp.), and penetrometer B type (Konica Medical Corp.).
After irradiating X-rays via S.R.
The DF treatment liquid (both manufactured by Konica Corporation) was used for a total treatment time of 25 seconds. The SRX-503 automatic processor was modified so that the processing time was as shown below, and the replenishment amount of the processing solution was 21 for both developer and fixer.
It was treated with 0 ml / m ² and 170 ml / m ^2.

Development time: 8 seconds Fixing time: 6.3 seconds
Washing time: 3.4 seconds Between washing and drying (squeeze): 2 seconds Drying time:
5.3 seconds Total processing time: 25 seconds (sensitivity) Sensitivity was shown as a relative value when the reciprocal of the X-ray exposure amount required for sample 1 to obtain the minimum density +0.1 was set to 100.

(Evaluation of Residual Color) With respect to the unexposed sample, sensitometric evaluation was carried out in the same manner, and the residual color contamination was visually evaluated in the following 5 grades.

5: No pollution 4: Slightly polluted 3: Slightly polluted but practically usable 2: Slightly polluted and practically limited 1: Practically polluted and practically unusable The results are shown in Table 1.

[0056]

[Table 1]

From the results shown in Table 1, it can be seen that the samples of the present invention have high sensitivity and have little residual color contamination, and good results can be obtained.

Example 2 The spectra of potato potato starch and acid-treated gelatin were compared.

2 g / l acid-treated gelatin solution and 2 g / l
The absorbance of 1 of potato solution of potato was measured at a wavelength of 200 to 400 nm. Potato starch solution showed almost no absorption in this range, while gelatin solution showed large absorption below 250 nm. FIG. 1 is a graph showing the absorbance for these wavelengths.

From this, it is clear that the absorption of potato potato starch at 200 to 400 nm is less than that of gelatin, and the influence of the absorption of silver halide in the wavelength region on the decrease in sensitivity is small.

[0061]

The present invention has made it possible to provide a silver halide photographic light-sensitive material which has high sensitivity even in rapid processing and has less residual color.

[Brief description of drawings]

FIG. 1 is a graph showing wavelength-absorbance of gelatin and starch.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, and at least one light-sensitive silver halide emulsion layer. Contains silver halide grains having a silver chloride content of 50 mol% or more, and the absorbance in the wavelength region of 200 to 400 nm is less than 1.0 in the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising a hydrophilic polymer.