JPH0764220A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To restrain the occurrence of roller marks and to enhance sharpness by specifying each composition of an emulsion layer and its emulsion and a support. CONSTITUTION:The emulsion layer comprises flat silver halide grains having an aspect ratio of 1-5 and amounting to at least >=50% of the projection areas of the total silver halide grains and this emulsion is spectrally sensitized with the compounds represented by formulae I and/or II in which each of Z1 and Z2 is a nonmetallic atomic group necessary to form a benzo- or naphtho-xaZole ring; each of R1 and R2 is alkyl or aralkyl; X is a charge-balancing counter ion; n is 0 or 1; each of R3 and R4 is 1-5 C alkyl or the like; and each of V1 and V2 is H, alkyl, or the like. The support comprises the copolymer of terephthalic acid and ethylene glycol and the compound represented by formula III in which R5 is 1-20 C alkyl or the like; L is 0 or the like; Y is -CO2- or the like; X1 is -CON(R6)R7 or the like; R6 is H or alkyl; and R7 is H, cycloalkyl, or the like.

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, more specifically, a silver halide photographic light-sensitive material having improved sharpness and less roller marks even at high temperature rapid processing without development hardening. Regarding

[0002]

2. Description of the Related Art Conventionally, in medical light-sensitive materials, the sharpness of images on X-ray films is extremely important in order to detect fine lesions at an early stage and appropriately diagnose them.

As a conventional sharpness improving means, for example,
A water-soluble dye is contained in the photosensitive layer and its adjacent layer (Japanese Patent Laid-Open No. 50-28827, Japanese Patent Laid-Open No. 57-185038, Japanese Patent Laid-Open No. 1-158430), but these cause a decrease in sensitivity. , Increase in radiation dose.

Further, when a high-sensitivity intensifying screen is used, graininess is deteriorated and total image quality is deteriorated.

When the main cause of sharpness deterioration is crossover light, it is considered that the emulsion is coated not on both sides but on only one side, but this method softens the photographic characteristics and processing. There is a large amount of residual silver and residual hypo after that, and deterioration (discoloration) of the silver image occurs when left after development, which is not preferable.

On the other hand, the use of tabular silver halide grains as a means for improving image quality has hitherto been described, for example, in British Patent No. 2,112,157, US Patent Nos. 4,439,520 and 4,433,048.
No. 4,414,310, and No. 4,434,226.

However, the tabular silver halide grains have a drawback that they are easily blackened by pressure, and in particular, in processing by an automatic developing machine, a processing failure at the time of development, which is called a roller mark, is liable to occur, which results in image quality. It had a great adverse effect.

As a means for improving this, there has been reported a method in which the structure of silver halide grains is made to have a high iodine inside, or gelatin or latex is used. Pressure desensitization occurs, and the desensitized portion on the diagnostic film is likely to be mistaken for a lesion, and is avoided in the market.

Further, when gelatin or latex is used, the amount of the binder is increased, so that there is a defect that the drying property of the light-sensitive material is deteriorated during the development processing.

Further, in recent years, in order to improve the working environment, it has been desired to reduce the odor generated from the processing liquid, and the processing without the development hardening agent such as glutaraldehyde has become popular in the market. In this developer, the roller mark, which is a pressure mark in the developer by the roller, is extremely deteriorated, and improvement has been desired.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which solves the above-mentioned drawbacks and has an improved roller mark and improved sharpness.

[0012]

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 on both sides of a transparent support. Is a tabular silver halide emulsion in which at least 50% or more of the projected area has an aspect ratio of 1 or more and less than 5, and the emulsion is spectrally sensitized with a compound of the following general formula [1] and / or [2]. And the support is terephthalic acid, ethylene glycol and the following general formula [3]
It is achieved by a silver halide photographic light-sensitive material characterized by comprising a copolymer with a compound represented by

The present invention will be described in detail below.

[0014]

[Chemical 3]

[In the formula, Z ₁ and Z ₂ each represent a non-metal atomic group necessary for completing a benzoxazole nucleus and a naphthoxazole nucleus. R ₁ and R ₂ each represent an alkyl group or an aralkyl group. X is a charge balance counter ion, and n represents 0 or 1. R ₃ and R ₄ are respectively substituted,
Unsubstituted alkyl group having 1 to 5 carbon atoms, 5 to 6 carbon atoms
Represents a substituted or unsubstituted aryl group, V ₁ and V ₂ each represent a hydrogen atom, and a substituted or unsubstituted alkyl group and alkoxy group. ]

[0016]

[Chemical 4]

[Wherein R ₅ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 7 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 12 carbon atoms] Represents an unsubstituted aryl group, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 3 to 10 carbon atoms, and a hydrogen atom.

L represents an oxygen atom or a divalent linking group, and Y
Is -CO ₂ -, - it represents a CON (R _6).

X ₁ represents --CON (R ₆ ) R ₇ , --CO ₂ R ₇ or --SO ₂ R ₈ , and R ₆ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. .

R ₇ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 7 carbon atoms, a substituted or unsubstituted carbon atom having 6 to 12 carbon atoms. A substituted aryl group, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted alkynyl group having 3 to 10 carbon atoms are shown.

R ₈ represents a hydrogen atom or a phenyl group which may be substituted or unsubstituted. ] The average grain size of tabular silver halide grains according to the present invention is 0.3
˜3.0 μm is preferable, and 0.5 to 1.5 μm is particularly preferable.

The tabular silver halide grain of the present invention has an average value of grain diameter / thickness (called aspect ratio) (called average aspect ratio) of 1 to 5, preferably 1.5 to
4, particularly preferably 2-3.

The average thickness of the tabular silver halide grains of the present invention is preferably 0.5 μm or less, particularly preferably 0.3 μm or less.

In the present invention, the diameter of the silver halide grain is defined as the diameter of a circle having an area equal to the projected area of the grain from the observation of an electron micrograph of the silver halide grain. In the present invention, the thickness of a silver halide grain is defined as the minimum distance between two parallel planes constituting a tabular silver halide grain.

The thickness of tabular silver halide grains can be determined from electron micrographs of silver halide grains with shadows or electron micrographs of sample slices obtained by coating a support with a silver halide emulsion and drying. .

To obtain the average aspect ratio, the minimum
Measure 100 samples. In the silver halide emulsion of the present invention, the effect is obtained when the tabular silver halide grains account for 50% or more of all the light-sensitive silver halide grains.

The emulsion used in the present invention may be a single emulsion or a mixture of two or more kinds of emulsions.
The emulsions to be mixed may be emulsions according to the present invention, or may be normal crystals or twinned grains having an aspect ratio of less than 2.

The tabular silver halide emulsion of the present invention is preferably monodisperse, and the average grain size is ±
It is particularly preferable that the silver halide grains contained in the grain size range of 20% are 50% by weight or more.

The tabular silver halide emulsion of the present invention may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but it has a high sensitivity. Silver iodide or silver iodobromide is preferable, and the average silver iodide content is 0 to 5.
It is 0 mol%, particularly preferably 0.1 to 3.0 mol%.

The tabular silver halide emulsion of the present invention comprises
The halogen composition may be uniform within the grain or silver iodide may be localized, but those localized in the central portion are also preferably used.

The method for producing a tabular silver halide emulsion is described in, for example, JP-A Nos. 58-113926, 59-113927, and 58-113934.
No. 62-1855, European Patents 219,849, 219,85
You can refer to No. 0 etc. A method for producing a monodisperse tabular silver halide emulsion is disclosed in JP-A-61-664.
Reference can be made to Publication No. 3.

As a method of producing a tabular silver iodobromide emulsion having a high aspect ratio, a silver nitrate aqueous solution or a silver nitrate aqueous solution and a halide aqueous solution are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to generate seed crystals. And then grown by the double jet method.

The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the rate of addition of an aqueous silver salt and halide solution. The aspect ratio is calculated by the seed crystal preparation method, the thickness and the pAg, pH, and halogen composition during growth.
It can be controlled by aging time and temperature.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

Further, for the tabular silver halide grains, a silver halide solvent such as ammonia, thioether or thiourea can be used at the time of production, if necessary. The grain growth may be carried out by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions, or may be supplied as fine particles of silver halide. In this case, a combination of silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a halogen ion-containing solution, a silver ion-containing solution and the like can be supplied.

The silver halide emulsion according to the present invention includes
Core / shell type or double structure type grains having a silver halide composition whose surface is different from the inside of the grain are also preferably used. Regarding the core / shell type particles, JP-A-59-177535
Particles can be prepared by the method described in Nos. 59-178447, 60-35726, 60-147727 and the like.

The emulsion may be subjected to a water washing method such as a Noudel water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication Sho
Particularly preferred desalting method is a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in 35-16086, or a method using an aggregating polymer agent described in JP-A-63-158644, such as G3 and G8. As.

The chemical sensitization method includes so-called sulfur sensitization,
Sensitization with selenium compounds, sensitization with tellurium compounds, gold sensitization, noble metals of Group VIII of the periodic table (eg Pd, Pt, Ir
And the like, and a combination of these sensitization methods can be used. Of these, a combination of gold sensitization and sulfur sensitization, or a combination of gold sensitization and a selenium compound is preferable. Further, it is also preferable to use it in combination with reduction sensitization.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of chemical sensitization from the viewpoint of sensitivity and dye adsorption. A method of adding in the form of fine grains of silver iodide is particularly preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide.

The compounds are particularly preferably azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having a mercapto group or a compound having a benzene ring.

The silver halide photographic light-sensitive material according to the present invention is subjected to a reduction treatment, a so-called reduction sensitization method, in which a reducing compound is added, and a silver ion excess state of pAg = 1 to 7 called silver aging is passed. Method, called high pH aging
It may be applied to the silver halide emulsion by a method of passing a high pH state of pH = 8 to 11, or the like. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. The reducing compound may be an inorganic or organic compound, such as thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, and sulfite. Examples thereof include salts, and particularly preferable examples include thiourea dioxide, stannous chloride and dimethylamine borane.

The amount of these reducing compounds added varies depending on the reducing properties of the compound and the emulsion production conditions such as the type of silver halide and the dissolution conditions, but it is 1 × 10 ^-8 to 1 × 10 1 per mol of silver halide. A range of ^-2 mol is suitable. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

The silver halide photographic light-sensitive material of the present invention comprises
Spectral sensitization is carried out using the spectral sensitizing dyes of the above general formula [1] or [2].

Next, specific examples represented by the general formula [1] will be shown. However, the present invention is not limited to the following compounds.

[0047]

[Chemical 5]

[0048]

[Chemical 6]

[0049]

[Chemical 7]

Next, a specific example represented by the general formula [2] will be shown. However, the present invention is not limited to the following compounds, and compounds described in JP-A-5-11389, JP-A-4-291338 and the like can also be used.

[0051]

[Chemical 8]

[0052]

[Chemical 9]

These sensitizing dyes may be used alone or in combination. Sensitizing dyes are often used in combination. Examples of using a combination of sensitizing dyes include U.S. Pat.Nos. 2,688,545 and 2,9
77,299, 3,397,060, 3,522,052, 3,
No. 527,641, No. 3,617,293, No. 3,628,964, No.
No. 3,666480, No. 3,679,428, No. 3,703,377, No. 3
3,837,862, British Patent 1,344,281, Japanese Patent Publication No. 43-4936
It is described in the official gazette.

The sensitizing dye can be added at any time during grain formation, before and after chemical sensitization, during the sensitization, and before coating, but it is preferably added before the completion of chemical sensitization. Of course, it can be added to several places.

The preferred addition amount is 40 mg / mol Ag to 400 mg
/ MolAg is preferably used. More preferably, 80 mg
/ MolAg to 200 mg / molAg is preferably used.

Gelatin is preferably used as the hydrophilic colloid or binder used in the light-sensitive material of the present invention, but other hydrophilic colloids can be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, dextran and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. In particular, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5000 to 10,000 together with gelatin. Examples of these are, for example, JP-A-1-307738, 2-62532, 2-24748, 2-
44445, 1-66031, JP-A-64-65540, 63-10184
No. 1, 63-153538 and the like.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin as described in Bull. Soc. Sci. Phot. Japan, No. 1630 (1966), as well as gelatin derivatives (gelatin such as acid. Halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, those obtained by reacting various compounds such as epoxy compounds) Included.

The compound represented by the general formula [3] of the present invention is a 1-alkyl-2-cyano-3-alkoxyphenol according to the method described in World Patents WO-93 / 05443 and 93/05444. Synthesize an acrylate and by ether reaction with dimethyl benzene-1,4-dicarboxylate, or
The monomer can be synthesized using a known reaction such as a reaction with an epoxide.

The support copolymerized using these is added when the dimethyl benzene-1,4-dicarboxylate and ethylene glycol are polymerized and copolymerized and melt-extruded, and the two directions, horizontal and horizontal. It can be stretched to obtain a support.

Next, specific examples of the general formula [3] of the present invention will be shown, but the present invention is not limited to the following compounds, and the compounds described in WO-93 / 05443 are used. You can

[0062]

[Chemical 10]

[0063]

[Chemical 11]

When the compound of the general formula [3] is used to copolymerize ethylene glycol and terephthalic acid, the weight ratio is preferably 1: 1 with respect to terephthalic acid used for the polymerization.
It is 1,000, more preferably 1: 10,000.

The support used in the present invention is preferably a support made of polyethylene terephthalate, but polyethylene naphthalate is used in order to improve the sharpness and to reduce the weight of the film by thinning the base. When copolymerizing or using a polyethylene naphthalate base, 1-alkyl-2 should be prepared according to the above method.
-Cyano-3-alkoxyphenol acrylate was synthesized, and the monomer was synthesized by an ether reaction with dimethyl 2,6-dicarboxylate or using a known reaction such as a reaction with epoxide, and naphthalene-2,6- It may be copolymerized with dicarboxylic acid and ethylene glycol.

In order to improve the adhesion of the coating layer, the surface of these supports is preferably provided with an undercoat layer, corona discharge, ultraviolet ray irradiation or the like.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978),
The compounds described in No. 18716 (November 1979) and No. 308119 (December 1989) are mentioned. The types of compounds and the places where they are described in these three Research Disclosures 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 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 Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 VIII Plasticizer 27 VII 650 Right 1006 XII Sliding agent 27 VII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IV The photographic processing of the light-sensitive material of the present invention can be carried out, for example, by RD-17643 described above.
XX-XXI, pages 29-30, or 308119 XX-XXI, 1011-
Treatment with a treatment liquid as described on page 1012 may be performed. This process may be a black and white photographic process that forms a silver 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.
It should be noted that the developer may be a known one such as preservative, alkaline agent, p
An H buffer, an antifoggant, a development accelerator, a surfactant, an antifoaming agent, a toning agent, a water softener, a dissolution aid, a viscosity imparting agent and the like may be used if necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0071]

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

Example 1 (Preparation of seed emulsion) A seed emulsion Em-A having a high degree of monodispersity was prepared by the following method.

A1 Hydrogen peroxide treated ossein gelatin 11.3 g Potassium bromide 6.72 g DF-1 1.2 ml Water to make 1.13 l

[0074]

[Chemical 12]

B1 silver nitrate 170 g water to 227.5 ml C1 ossein gelatin 4.56 g potassium bromide 119 g water to 227.5 ml D1 ammonia water (28%) 66.6 ml A1 liquid vigorously stirred at 40 ° C. C1 liquid was added by the double jet method to generate nuclei. After the addition, the temperature of the mixed solution was lowered to 20 ° C., the potential was adjusted to 40 mV, D1 was added in 20 seconds, and aging was carried out for 5 minutes.

Then, modified gelatin (substitution rate 80%) in which the amino group of gelatin was substituted with a phenylcarbamoyl group was used.
g, and after stirring, the pH was lowered to 3.0 to cause aggregation, and the upper portion was decanted. 2000 ml of water was added again, the pH was raised to 6.0, and the mixture was stirred and dispersed. After that, the pH was lowered to 3.0 and decantation was performed in the same manner.

Further, 23 g of ossein gelatin was used to redisperse the seed emulsion washed with water.

When the seed emulsion was observed with an electron microscope,
It was a monodispersed AgBr emulsion having an average grain size of 0.28 and a width of 20%.

(Preparation of tabular grains) A silver halide emulsion Em-1 mainly composed of tabular twin crystals was prepared by using the seed emulsion Em-a and the solution shown below.

[0080] E1 ossein gelatin _{6.49g HO - (- CH 2 CH} 2 O) m _{[CH (CH 3) (CH-} CH 2 O) 17 ] _{- (CH-CH 2 O)} 17 - (CH 2 CH 2 ) -nH 10% methanol solution 1.2 ml Equivalent to 0.62 mol of the seed emulsion F1 ossein gelatin 1.69 g potassium bromide 107.2 g potassium iodide 2.30 g water 504 ml G1 silver nitrate 170 g water 504 ml violently at 65 ° C To the above stirred E1 solution, F1 solution and G1
The solution was added by the control double jet method. The addition flow rate was controlled to 80% of the flow rate at which new nuclei were generated. During the addition, the potential was kept at −10 mV at 65 ° C. by using a controlling KBr aqueous solution.

After the addition was completed, the pH was adjusted to 6.0, the sensitizing dyes shown in Table 1 (or the respective dyes were entered) were added as spectral sensitizing dyes, and after sufficient adsorption,
Precipitation, desalting, and washing with water were performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate.

Furthermore, using 23 g of ossein gelatin,
The above emulsion washed with water was redispersed. The emulsion had a potential at 50 ° C. of 50 mV and a pH of 5.85.

About 3000 Em-1 particles were observed and measured by an electron microscope to analyze the shape. The results were as follows.

Ratio of hexagonal flat plate to total projected area; 80% Average particle diameter of hexagonal flat plate crystal (converted to circle) 1:40 μm Average particle thickness of hexagonal flat plate crystal; 0.7 μm Average aspect ratio of hexagonal flat plate; 2.0 Dispersity: 15% The amount of seed emulsion used was adjusted, and other than that, Em-2 and 3 were adjusted in the same manner as in the above Em-1. However, the amount of the above-mentioned sensitizing dye added before desalting was adjusted to an amount proportional to the calculated surface area of the particles.

About 3000 particles of Em-2 and 3 were observed and measured by an electron microscope to analyze the shape. The results were as follows.

Ratio of hexagonal plate to total projected area: 80%, respectively Average particle diameter of hexagonal plate crystal (converted to a circle); Em-2: 1.1μ
m, Em-3: 0.6 μm Average grain thickness of hexagonal tabular crystal; Em-2: 0.55 μm, Em-
3: 0.3 μm Average aspect ratio of hexagonal tabular plate; 2.0 Dispersion of hexagonal tabular plate; each 15% Chemical sensitization of tabular emulsion Em-1 1% NH ₄ SCN per 1 mol of silver in Em-1 prepared above.
5.2 ml, 0.2% HAuCl ₄ ; 0.78 ml, 0.25% Na ₂ S ₂ O ₃ ; 5.6 m
Immediately before the addition of the chemical sensitizer consisting of l, the spectral sensitizing dyes shown in Table 1 were added and chemical sensitization was performed at 48 ° C.

30 minutes after the start of chemical sensitization, the average particle size is 0.04 μm.
0.002 mol of AgI fine particles was added per mol of silver halide. After further chemical aging for 20 minutes, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene to silver halide 1
2.4 g was added per mol, and the temperature was lowered to stop the chemical aging.

With respect to Em-2 and 3, chemical sensitizers and sensitizing dyes proportional to the surface area of the grains were added and chemical ripening was performed in the same manner as Em-1.

When liquid B1 and liquid C1 were added to liquid A1 by the double jet method to generate nuclei, D1 was added for 20 seconds by changing the temperature and potential of the mixed liquid after the addition and aged for 5 minutes. Was carried out to prepare emulsions having aspect ratios of 1 to 6.

Preparation of coating liquid The emulsion chemically ripened as described above was added with Em-1: Em-2: Em-3 at 30: 5.
After mixing at a ratio of 0:20, the following various additives were added to prepare a coating emulsion solution.

Coating liquid additive 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-triphenyl -Phosphonium chloride 50 mg 1,3-dihydroxybenzene-4-ammonium 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

[0092]

[Chemical 13]

The following additives were added to the silver halide emulsion coating prepared above on both sides of the support of the present invention which had been undercoated for emulsion coating, and the resulting coating solution was coated.

The coated silver amount was 2.5 g / m ^{2 on} one side and the gelatin amount was 3.0 g / m ² .

The additives used in the protective layer solution are as follows. The addition amount is shown as the amount per 1 g of gelatin.

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

[0097]

[Chemical 14]

Glyoxal 15 mg / g Gel The obtained sample was treated with the following developing solution and fixing solution using an automatic processor SRX-503 (manufactured by Konica Corporation).

Developer Formulation Part-A (for finishing 10.8 liters) Potassium hydroxide 340 g Potassium sulfite (50% solution) 2150 g Diethylenetetraamine pentaacetic acid 32.3 g Sodium hydrogencarbonate 108 g 5-Methylbenzotriazole 150 mg 1-phenyl-5- Mercaptotetrazole 15mg Hydroquinone 280g Add water to finish to 3600cc Part-B (10.8 liter finish) Glacial acetic acid 158g Triethylene glycol 144g 1-Phenyl-3-pyrazolidone 19.5g 5-Nitroindazole 0.32g n-Acetyl-D, L -Penicillamine 0.11g Part-A and Part-B were mixed and made up to 10.8 liters with water.

Starter formulation (for 1.0 liter finish) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Water was added to 1.0 l To finish.

Starter is 20c per 1.0 liter of developer
c added.

Fixer formulation Part-A (for finishing 16.4 liters) Ammonium thiosulfate (70 wt / vol%) 3460 g Sodium sulfite 150 g Sodium acetate trihydrate 350 g Sodium citrate 43 g Gluconic acid 33 g Boric acid 26 g Glacial acetic acid 120 g Part-B (For finishing 16.4 liters) Aluminum sulphate 56g Sulfuric acid (50wt%) 91g Part-A and Part-B were mixed and made to 16.4 liters with water.

Treatment process Process temperature (° C) Treatment time (sec) Replenishment amount Insertion − − 1.2 Development + crossover 35 14.6 270cc / m ² Fixing + crossover 33 8.2 430cc / m ² Washing + crossover 18 7.2 7.0l / min Squeeze 40 5.7 Drying 50 8.1 Total-43.8 The capacity of each tank of the automatic processor used was 16 liters for the developing tank,
The fixing tank is 10 liters and the washing tank is 10 liters.
O ₂ , Al ₂ O ₃ , Ag + ion ceramic particle size 1.0 to 1.5 m
m, specific gravity 2.5-2.6) 200 g was filled in a bag sewn with a 20-mesh polyethylene woven cloth, and immersed in the vicinity of the washing water supply part of the washing tank. For drying, an infrared heater (heater temperature 220 ° C) and warm air (60 ° C) were used together.

An infrared sensor was used to detect the insertion of the film. The film area for 10 quadrants was detected, and the replenishment amount for 10 quadrants (developer 210 cc, fixer 320 cc) was replenished.

(Evaluation of Sharpness) The above coated sample was sandwiched between intensifying screens for X-ray photography (for aurora LT-2 regular) and a phantom for the chest placed at a distance of 2 m from the X-ray tube. I took a picture. The shooting conditions were 90 kVP and 50 mA, but the irradiation time was adjusted so that the concentration in the lung field was 1.8. Then, the development processing described above was performed, and the sharpness of the lung field and the depiction of the mediastinum of the film processed on Schaukasten were evaluated.
In each case, the evaluation was done on a 5-point scale. 5 is the highest level, 3 is the diagnostically acceptable limit level, and levels less than 3 are levels that cannot be practically used for diagnosis.

(Evaluation of Roller Mark) The blackening failure due to the pressure of the roller of the automatic developing machine at the time of development was evaluated as follows. After the obtained sample was exposed to a density of 1.5, the surface of the roller was roughened and the above processing was carried out using an automatic developing machine equipped with a roller having a roughened surface. The roller mark after the treatment was visually evaluated. Rank 5 is a level where roller marks are not generated, Rank 3
Indicates the lowest level of occurrence in the market, and Rank 1 indicates the number of occurrences.

The results are shown below.

No. A ratio Sensitizing dye General formula [3] Sharpness roller Remark Compound. Addition amount Compound addition ratio Mark No. (mg / molAg) (to TFA ratio) (rank) 1 2----1 1 Comparison 2 2 I-1 120--1 4 〃 3 2--III-1 100: 1 2 1 〃 4 2 II-1 120--1 5 〃 5 2 I-1 120 III-1 100: 1 5 5 Invention 6 2 II-1 120 III-1 100: 1 5 5 〃 7 2 I-1 60 III-1 100: 1 4 4 〃 8 4 I-1 80 III-1 100: 1 4 3 〃 9 5 I -1 100 III-1 100: 1 5 2 Comparison 10 6 I-1 160 III-1 100: 1 5 1 〃 11 2 I-1 200 III-1 100: 1 4 5 Invention 12 2 I-1 400 III -1 100: 1 45 5 〃 16 2 I-1 120 III-1 50: 1 5 5 〃 17 2 I-1 120 III-1 500: 1 4 5 〃 18 2 I-1 120 III-1 1000: 1 3.5 5 〃 19 2 I-2 120 III-2 100: 1 5 5 〃 20 2 I-5 120 III-3 300: 1 5 5 〃 21 2 I-8 120 III-4 500: 1 5 5 〃 22 2 II-3 120 III-7 100: 1 5 5 〃 23 2 II-4 200 III-8 300: 1 5 5 〃 24 2 II-7 180 III-2 500: 1 4 5 〃 25 2 II-10 120 III -2 1000: 1 3.5 5 〃 Note: The addition amount in the above general formula [3] (ratio to TFA) is the polymerization with terephthalic acid. Saying the ratio Note: The above A ratio means the aspect ratio.

From the above results, it is understood that the present invention can improve the roller mark and obtain an image in which the sharpness of the lung field is improved.

[0110]

The silver halide photographic light-sensitive material according to the present invention has excellent roller marks and sharpness.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on both sides of a transparent support, the emulsion layer having an aspect ratio of at least 50% or more. It comprises a tabular silver halide emulsion having a ratio of 1 or more and less than 5, and said emulsion is spectrally sensitized with a compound of the following general formula [1] and / or [2], and said support is terephthalic acid. , A silver halide photographic light-sensitive material comprising a copolymer of ethylene glycol and a compound represented by the following general formula [3]. [Chemical 1] [In the formula, Z ₁ and Z ₂ each represent a non-metal atom group necessary for completing a benzoxazole nucleus and a naphthoxazole nucleus. R ₁ and R ₂ each represent an alkyl group or an aralkyl group. X is a charge balance counter ion, and n represents 0 or 1. R ₃ and R ₄ each represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 5 to 6 carbon atoms, and V ₁ and V ₂ each represent a hydrogen atom, A substituted or unsubstituted alkyl group and alkoxy group are shown. ] [Chemical 2] [Wherein R ₅ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 7 carbon atoms, a substituted or unsubstituted C 6 to 12 carbon atom] Aryl group, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms,
It represents a substituted or unsubstituted alkynyl group having 3 to 10 carbon atoms and a hydrogen atom. L represents an oxygen atom or a divalent linking group that may or may not be present, and Y represents —CO ₂ — or —CON (R ₆ ). X ₁ is _{-CON (R 6) R 7,} -CO 2 R 7 or -SO
₂ represents R ₈ and R ₆ represents hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ₇ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 7 carbon atoms, or 6 carbon atoms
A substituted or unsubstituted aryl group having 12 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted alkynyl group having 3 to 10 carbon atoms are shown. R ₈ represents a hydrogen atom or a substituted or unsubstituted phenyl group. ]