JPH05289233A - Silver halide photographic sensitive material high in sharpness - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material freed of residual dye stains and capable of forming an image high in sharpness with high sensitivity and good in film conveyability and not causing vacuum sucking plate marks and the like in an automatic developing machine. CONSTITUTION:The silver halide photographic sensitive material has at least each one silver halide emulsion layer on both sides of a transparent support, and it is exposed to light and developed, and when the exposure gives one side a density of fog +1.60, it gives the other side a density of fog <=+0.20 in the same exposure position as that of the reverse side, and the high density side is higher in sensitivity than the reverse low density side. A protective layer on the silver halide emulsion layer contains at least each one of specified anionic and cationic fluorinated surfactants.

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, and more particularly to a silver halide photographic light-sensitive material having no residual color contamination, high sensitivity, excellent image sharpness and good transportability. is there.

[0002]

BACKGROUND OF THE INVENTION An X-ray film used for medical diagnosis is generally sandwiched between two fluorescent intensifying screens sandwiching the film and held in a cassette to form an image. That is, considering the effect of X-rays on the human body, the front photographic emulsion layer is exposed to light by the front intensifying screen excited by X-rays, and then excited by the X-rays transmitted through the front, and then the surface intensifying screen. The X-ray image is formed by exposing the emulsion on the back side with the exciting light of (1) to effectively use the X-ray.

In recent years, X-ray diagnostic films and intensifying screens have been improved in sensitivity and image quality, and in particular, sharpness is strongly desired because it is necessary to know the state of a lesion or an affected area in more detail.

In a film having an emulsion layer on both sides of a support, light emitted from one intensifying screen passes through an adjacent emulsion layer and is further diffused by the support to form an image-like image on the opposite emulsion layer. Exposure is given to cause a phenomenon of so-called crossover exposure, which is a factor that deteriorates the sharpness of an image.

In order to reduce crossover exposure and improve sharpness, many proposals have been made in the past, for example, JP-A-61-132945 in which a dye is contained in a silver halide emulsion layer or a constituent layer. Alternatively, there is British Patent 821,352.

Further, an intensifying screen used in combination with a film has been improved. For example, silver halide emulsions having different color sensitivities are provided on the A side and the B side, and fluorescence having an emission spectrum matching each of the color sensitivities is provided. It is disclosed in Japanese Patent Application Laid-Open No. 2-110538 using an intensifying screen.

However, these improved techniques cannot avoid deterioration of sharpness as long as two intensifying screens are used with double-sided emulsion, and particularly in an X-ray photographing system, an oblique incidence photographing method in which X-rays are obliquely incident on the film surface. On the other hand, the deviation of the images on both sides significantly deteriorates the sharpness.

Further, an attempt has been made to provide an emulsion layer only on one side for high sharpness and perform exposure from only one side. However, this method has low sensitivity, and if one tries to increase the sensitivity only on one side. This inevitably leads to an increase in the film thickness of the photosensitive emulsion layer, and as a result, performance such as developability, fixability, water washability, and dryness deteriorates, and image contamination is caused by color residue, residual silver, residual hypo, etc. It is also not preferable because it causes a trouble such as deterioration of transportability due to poor drying.

In the silver halide photographic light-sensitive material having silver halide emulsion layers on both sides, the inventors of the present invention have an emulsion layer (A) side on one side and an emulsion layer (B) side on the other side. As a result of various studies on the method of improving the sharpness by using the fluorescent intensifying screen only from one side by changing the sensitivity and the coated silver amount, a photographic light-sensitive material excellent in sharpness and processability was obtained. As compared with the method of coating layers, it was necessary to coat a slightly higher amount of emulsion on the high-sensitivity surface, and as a result, it was found that there are problems in residual color property, transportability and the like.

Particularly in terms of transportability, it has been regarded as one of the important performances in recent years because the X-ray film photographing system is automated.

That is, a fog caused by a vacuum suction cup used for automatic conveyance and automatic peeling, that is, a so-called sucker mark is apt to occur on the (A) surface having high sensitivity, and its solution has been desired.

[0012]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material for X-rays, which has no residual color contamination, high sensitivity, and a high sharpness image which is free from image shift even in oblique incidence photography. Is to provide.

A second object of the present invention is to provide the above-mentioned silver halide photographic light-sensitive material for X-ray which does not generate a vacuum suction cup mark during automatic film transport. Other objects will be apparent from the following specification.

[0014]

The above objects of the present invention are: (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on both sides of a transparent support, the light-sensitive material is exposed and developed. When the exposure amount is an exposure amount that gives a density of fog +1.60 to one surface, the density at the corresponding exposure position on the other surface is fog +0.20 or less, and the higher density side is used. Of the fluorinated anionic surfactant represented by the following general formula [1] in the protective layer on the silver halide emulsion layer. A silver halide photographic light-sensitive material containing one kind and at least one kind of a fluorine-based cationic surfactant represented by the following general formula [2].

(2) A method of forming an image by exposing from the high-sensitivity side of the light-sensitive material with light having a wavelength of 300 nm or more, which has a latent image forming ability, and developing it to form an image. The amount of transmitted light reaching the interface between the support and the low-sensitivity emulsion layer is 12% or more and 75% or less of the exposure to the high-sensitivity surface.
It is achieved by the silver halide photographic light-sensitive material described in the item (1).

In the general formula [1] (Cf)-(Y) _n , Cf is at least 3 fluorine atoms and at least 2
Represented by an n-valent group containing carbon atoms, Y is -COOM, -SO
Represents ₃ M, -OSO ₃ M or -P (= O) (OM) ₂ . M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2.

In the present invention, the fluorine-based anionic activator represented by the general formula [1] is particularly preferably the one represented by the following general formula [1a].

General formula [1a] Rf- (D) _t -Y In the formula, Rf represents a fluorine-substituted alkyl group or aryl group having 3 to 30 carbon atoms, and D is -O-, -COO-, -CON. (R ₁ )-or —SO ₂ N (R ₁ ) — represents a divalent group having 1 to 12 carbon atoms and containing at least one bond. R ₁ represents an alkyl group having 1 to 5 carbon atoms, t is 1 or 2, Y is —COOM—, —S
Represents O ₃ M, —OSO ₃ M or —P (═O) (OM) ₂ , and M represents a hydrogen atom or an alkali metal or a cation such as a quaternary ammonium salt.

General formula [2] Rf'-L-X ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms,
At least one hydrogen atom is replaced by a fluorine atom. L represents a chemical bond or a divalent group. X ⁺ represents a cation and Z ⁻ represents a counter anion.

The present invention will be described in detail below.

Conventionally, in the case of an X-ray film having substantially the same emulsion on both sides of the support, a front surface image that directly enters the eye and an image of the back surface that passes through the support base and enters the eye during image observation (interpretation). Interpretation diagnosis is performed by adding and. In addition, in these X-ray photography, the X-ray incident angle is 90 degrees with respect to the film surface.
Although it is photographed so that the angle becomes °, the spread of the incident angle from the X-ray source (about 17 °) cannot be avoided even in this case. Further, in some cases, there is a case of photographing at an oblique incident angle, and in such a case, the "deviation" between the front and back images is further magnified, resulting in a marked decrease in sharpness.

As described above, the conventional system has been to perform image interpretation diagnosis in the form of integrating substantially even two-sided images. However, as a result of various studies, the present inventor found that the image is displayed on one side of the front and back depending on the density region. It was found that the image sharpness can be remarkably improved from the low density region to the medium density region by shifting to one side.

In the present invention, the emulsion layers are coated on both sides of the support, but unlike the conventional method, a difference in sensitivity is provided between the photosensitive emulsions on both sides to share the depiction density region to form an image, thereby improving sharpness. It is characterized in that The sensitivity of the emulsion layer on one side (A side) of the silver halide photographic light-sensitive material according to the present invention is 1.5 than that of the emulsion layer on the other side (B side).
It is necessary to be more than twice, preferably 2.0 to 10 times higher.

The surfactant is hereinafter simply referred to as "active agent".

Specific examples of the compounds represented by the general formula [1] and the general formula [1a] are shown below, but the present invention is not limited thereto.

[0026]

[Chemical 1]

[0027]

[Chemical 2]

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

Next, the fluorine-based cationic activator used in the present invention will be described.

In the general formula [2], Rf 'in the formula represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom is preferably substituted with a fluorine atom.

Rf 'is, for example, -C _k F _{k + 1} (k = 1 to 20,
3 to 12 are particularly preferable), -C _m F _2m , -C _m F _2m-1 (m = 2 to 2)
0, particularly preferably 3 to 12).

Examples of L include -SO ₂ N (R ¹ ) (CH ₂ ) _p- , -CON (R
¹ ) (CH ₂ ) _p- , -OASO ₂ N (R ¹ ) (CH ₂ ) _p- , -OACON (R ¹ ) (CH ₂ ) _p- ,
_{-OAO (CH 2) p -,} - OA (CH 2) p -, - O (CH 2 CH 2 O) q (CH 2) p -, - O (C
H ₂ ) p-, -N (R ¹ ) (CH ₂ ) _p- , -SO ₂ N (R ¹ ) (CH ₂ ) _p O (CH ₂ ) _r- , -CO
N (R ¹ ) (CH ₂ ) _p O (CH ₂ ) _r- , -OASO ₂ N (R ¹ ) (CHR ¹ ) _p OA-,-(CH ₂ )
_p (CHOH) _s (CH ₂ ) _r- and the like can be mentioned.

Examples of X ⁺ are -N ⁺ (R ¹ ) ₃ , -N ⁺ (CH ₂ CH ₂ OCH
₃ ) ₃ , -N ⁺ C ₄ H ₈ O (R ¹ ) ₃ , -N ⁺ (R ¹ ) (R ² ) (CH ₂ CH ₂ OCH ₃ ), -N ⁺ C _{5
^{H 5, -N + (R 1}} ) (R 2) (CH 2) p C 6 H 5, -N + (R 1) (R 2) (R 2) , and the like. Here, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent), p, r and s are each 0 to 6 and q is 1 to Twenty. A represents alkylene or arylene.

Examples of Z ⁻ include I ⁻ , Cl ⁻ , Br ⁻ , CH ₃ S
_{^{O 3 -, CH 3 -C 6}} H 4 -SO 3 - , and the like.

Specific examples of the fluorine-based cationic activator preferably used in the present invention will be given below, but the present invention is not limited thereto.

[0038]

[Chemical 6]

[0039]

[Chemical 7]

In the present invention, it is particularly preferable to use a fluorine-based cationic activator containing at least one bond of —SO ₂ N (R ¹ ) — which is hardly soluble. Here, the term “poorly soluble” means that 2.0 g of the activator was added to 100 cc of pure water at 23 ° C. and the mixture was stirred for 1 hour.
It becomes insoluble when a precipitate is formed or a floating substance is observed after standing for 24 hours.

For example, 2-1, 2-8, 2-15, 2-16 and the like correspond, but the present invention is not limited to these and can be divided by the above test.

The fluorine-based anionic activator or fluorine-based cationic activator according to the present invention is described in, for example, US Pat.
No. 751, No. 2,567,011, No. 2,732,398, No. 2,764,602
No. 2, No. 2,806,866, No. 2,809,998, No. 2,915,376,
2,915,528, 2,918,501, 2,934,450, 2,9
37,098, 2,957,031, 3,472,894, British Patent 1,
No. 143,927, No. 1,130,822, Japanese Patent Publication No. 45-37304, Japanese Patent Laid-Open No.
47-9613, 49-134614, 50-117705, 50-1177
No. 27, No. 50-121243, No. 52-41182, No. 51-12392,
Journal of the British Chemical Society (J. Chem. Soc.), 1950, 2789, 1957, 257.
4 and 2640, Journal of American Chemical Society (J. Amer. Chem. Soc.) Vol. 79 2
549 (1957), Oil Chemistry (J. Japan Oil Chemists Soc.) 12
Vol. 653, Journal of Organic Chemistry (J. Org. Chem.), Vol. 30, 3524 (1965)
, Etc.) and the like. Some of these fluorine-based activators are trade names of Megafac F from Dainippon Ink and Chemicals, Inc., and Fluorad from MN Mining and Manufacturing Company.
ad) FC under the trade name, Imperial Chemical Industry under the name Monflor, Ei DuPont Nemeras & Company under the name Zonyls, and Farbeberke Hoechst. They are each sold under the trade name of Licowet VPF by the company.

The total amount of the fluorine-based cationic activator and the fluorine-based anionic activator used in the present invention is preferably 0.1 to 1000 mg, preferably 0.5 to 300 mg, and more preferably 1.0 to 150 mg per 1 m ² .

When used in combination, two or more of each may be used in combination. Further, other fluorine-based nonionic activators, fluorine-based betaine activators, and hydrocarbon-based activators may be used in combination.

The addition ratio of the fluorinated anionic activator and the fluorinated cationic activator of the present invention is 1:10 to a molar ratio.
The ratio is preferably 10: 1, more preferably 3: 7 to 7: 3.

The location of addition of the fluorine-based anionic activator and the fluorine-based cationic activator of the present invention is preferably the surface protective layer of the silver halide emulsion layer. The activator of the present invention may be overcoated as a solution containing no binder on the surface layer of the light-sensitive material.

The sensitivity used in the present invention is basically determined by the light source for photographing the light-sensitive material used in the present invention.

For example, a regular X-ray film is measured by using a regular X-ray film photographing fluorescent intensifying screen, and an ortho X-ray film is measured by using an ortho X-ray film photographing fluorescent intensifying screen. If a system using another light source appears in the future, the light source used in combination with the light-sensitive material is used for measurement.

The value of sensitivity is given as the reciprocal of the X-ray dose required to obtain an optical density of 40% of the maximum density obtained by development. The measurement of the optical density is represented by the diffusion density in the optical system having the luminous efficiency spectral product distribution according to the ISO standard.

The total amount of silver halide on the side constituting the high-sensitivity layer of the light-sensitive material of the present invention is generally larger than that of the low-sensitivity layer in order to provide a difference in sensitivity. Therefore, it is necessary to form the highest possible concentration, and therefore it is necessary to increase the amount of silver halide attached to the high-sensitivity layer side.

As a constitution for achieving the object of the present invention, the total silver halide amount on the side constituting the high sensitivity layer is 1.1 to 5.0 times or more, preferably 1.2 times or more than that of the low sensitivity layer.
It is preferably 5.0 times or less. If it is more than that, the advantage of providing silver halide on both sides of the light-sensitive material for single-sided exposure as in the present invention is reduced.

In the silver halide photographic light-sensitive material of the present invention, the amount of light transmitted through the support and reaching the low-sensitivity surface (crossover light) upon single-sided exposure from the high-sensitivity surface is the usual X-ray amount. It is preferable that the amount is more than that of the double-sided light-sensitive material for line photography.
Practically, the transmitted light of the light source used is preferably in the range of 12% to 75%, more preferably 16% or more and 65% or less. This is because if the amount of transmitted light increases, the sharpness is deteriorated.

The emulsion used in the silver halide photographic light-sensitive material according to the present invention may be any silver halide such as silver iodobromide, silver iodochloride and silver iodochlorobromide, but high sensitivity is obtained. Silver iodobromide is preferable from the viewpoint that it can be obtained.

The silver halide grains in the photographic emulsion are isotropically grown grains such as cubes, octahedrons and tetrahedrons, or are polyhedral grains such as spheres, twins having plane defects. It may be composed of or a mixed type thereof. The grain size of these silver halide grains may be from fine grains of 0.1 μm or less to large grains of 20 μm.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 18716 (November 1979)
・ Pages 22 to 23 1.Emulsion Preparation and t
ypes), and (RD) No. 18716, page 684.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described, for example, in "Thethory of the photog" by TH James.
raphic process "4th edition, published by Macmillan (1977) 38
~ Method described on page 104, GF Daufin "Photoemulsion Chemistry"
"Photographic Emulsion Chemistry" published by Focal Press (1966), P. Glafikides "Physics and Chemistry of Photography" Chi
mie et Physique Photographique "published by Paul Montel
(1967), VL Zelikman et al. "Manufacturing and coating photographic emulsions".
"Making and coating photographic emulsion" Focal P
It is prepared by the method described in ress (1964).

That is, a solution method such as a neutral method, an acidic method or an ammonia method is mixed under conditions such as a forward mixing method, a back mixing method, a double jet method, a controlled double jet method or the like, a conversion method, a core / shell method. And the like, and a combination method thereof.

The silver halide emulsions preferably used in the present invention are, for example, JP-A-59-177535 and 61-116347.
Nos. 61-132943, 63-49751, and Japanese Patent Application No. 63-2382.
The internal high iodine type monodisperse particles disclosed in No. 25 and the like can be mentioned.

The crystal wall of the crystal may be a cubic, a tetradecahedron, an octahedron or an intermediate thereof in which (111) and (100) faces are arbitrarily mixed.

The monodisperse emulsion referred to herein means, for example, when the average particle diameter is measured by a conventional method, at least 95% of the particles by number or weight are within ± 40% of the average particle diameter, preferably within ± 30%. Is a silver halide grain. The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The definition of monodispersity described here is as follows.
It is described in JP-A-60-162244 and has a coefficient of variation of particle size of 0.20 or less.

The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. A preferred embodiment of the emulsion is a core / shell type monodisperse emulsion having a double structure consisting of a high iodine core portion and a low iodine shell layer. The silver iodide content of the high iodine portion is 20 to 40 mol%, and particularly preferably 20 to 30 mol.

The method for producing such a monodisperse emulsion is well known, and for example, J. Phot. Science 12, pp. 242 to 251 (1963), JP-A-4.
8-36890, 52-16364, 55-142329, 58-49938
No., British patent 1,413,748, U.S. patent 3,574,628, 3,
It is described in No. 655,394. A seed crystal is used as the monodisperse emulsion, and an emulsion in which grains are grown by supplying silver ions and halide ions using the seed crystal as a growth nucleus is particularly preferable.

As a method for obtaining a core / shell type emulsion, for example, British Patent 1,027,146 and US Pat.
No. 4,444,877, JP-A-60-14331, and the like. As another grain form used in the present invention, the silver halide emulsion is preferably tabular grains having an asbestos ratio of 3 or more.

The advantage of such tabular grains is that, for example, the spectral sensitization efficiency can be improved and the graininess and sharpness of the image can be improved. For example, British Patent 2,112,157 and US Pat.
No. 20, No. 4,433,048, No. 4,414,310, No. 4,434,226
No. 58-113927, No. 58-127921, No. 63-138342
No. 63-284272, No. 63-305343, etc., and the emulsion can be prepared by the method described in these publications.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image on the grain surface, an internal latent image type which forms a latent image inside the grain, or a type which forms a latent image on the surface and inside. It may be. These emulsions may use a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. 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. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or an aggregating polymer agent described in JP-A-63-158644, exemplified G3,
A particularly preferable desalting method is a method using G8 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 No. 17643 (December 1978), and N.
o. 18716 (November, 1979) and No. 308119 (December, 1989). The types and locations of the compounds shown in these three Research Disclosures are shown in the following table.

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 to 649 996 to 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 Interface Activator 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1009 XXII Support 28 XVII 1009 XVII Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643, page 28 and RD-308119, 1
Examples of suitable supports include plastic films, and the surface of these supports is provided with an undercoat layer to improve adhesion of the coating layer, corona discharge, or ultraviolet irradiation. Etc. may be given.

[0069]

EXAMPLES Examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 Preparation of Silver Halide Emulsion A silver iodobromide emulsion was prepared in which silver iodide was 1.3 mol% and the remaining 98.7 mol% was silver bromide. This emulsion has an average grain size of 1.
The average particle thickness was 4 μm, the average particle thickness was 0.34 μm, and the particle size dispersibility was 0.23 in terms of coefficient of variation (according to the method described in JP-A-60-162244). The obtained emulsion was designated as (A).

Separately, a silver iodobromide emulsion containing 1.2 mol% of silver iodide and the remaining 98.8 mol% of silver bromide was prepared. This emulsion had an average grain size of 1.2 μm, an average grain thickness of 0.27 μm and a grain size dispersibility of 0.22 in terms of variation coefficient. The obtained emulsion
(B).

Emulsions (A) and (B) have a total projected area of
90% or more was occupied by tabular grains having an aspart ratio of 3 or more. Preparation of Samples The resulting emulsions (A) and (B) were mixed with pure water such that the volume per mol of silver halide was 500 ml, and the temperature was raised to 50 ° C. to obtain the spectral sensitizing dye (a) described below. (b) was added in a weight ratio of 150: 1 so that the emulsion (A) was 300 mg and the emulsion (B) was 450 mg per mol of silver halide.

After 10 minutes, ammonium thiocyanate was added to the emulsion (A) at a concentration of 4 × 10 ⁻³ moles and the emulsion (B) at a concentration of 3 × 3 moles per mole of silver.
In addition to 10 ⁻³ mol, an appropriate amount of chloroauric acid and hypo were added to start chemical ripening. At this time, the pH was 6.15 and the silver potential was 80 mV. 15 minutes before the end of chemical ripening (70 minutes after the start of chemical ripening), add 30 parts of potassium iodide per mol of silver.
Add 0 mg, and after 5 minutes, add 10% (wt / vol) acetic acid to adjust the pH.
The pH was lowered to 5.6 and kept at that pH for 5 minutes, and then a 0.5% (wt / vol) solution of potassium hydroxide was added to return the pH to 6.15. Thereafter, 2500 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to complete the chemical ripening.

The following emulsion additives were added to the obtained emulsions (A) and (B) to prepare a preparation liquid. The pH of the photographic emulsion coating solution after preparation was 6.20 and the silver potential was adjusted to 80 mV (35 ° C.) using sodium carbonate and potassium bromide solutions.

A sample was prepared as follows using this emulsion coating solution. That is, the silver halide amount was set to the amount shown in Table 1 in terms of silver so that the photographic emulsion layer would have a gelatin amount of 2.1 g / m ² on both the high-speed emulsion layer side and the low-speed emulsion layer side. Further, exemplary compounds of the general formulas [1], [1a] and [2] were added as shown in Table 2, and a protective layer liquid was prepared by using the additives shown below. The protective layer and the emulsion layer prepared above so that the amount of gelatin attached would be 1.20 g / m ² were simultaneously coated on both sides of the support using two slide hopper type coaters at a speed of 85 m / min for 2 minutes. A sample was obtained by drying in 20 seconds. The support used was 3% of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt%.
Blue-colored polyethylene terephthalate film base with a thickness of 175 μm and a concentration of 0.15 coated with an aqueous dispersion of the copolymer obtained by diluting it so that the concentration of the copolymer consisting of two types of monomers would be 10 wt% Was used.

Spectral sensitizing dye (a) 5,5-dichloro-9-ethyl-3,3'-di- (sulfopropyl) oxacarbocyanine anhydrous sodium salt Spectral sensitizing dye (b) 5,5 ' -Di- (butoxycarbonyl) -1,1'-diethyl-3,3 '
-Anhydrous Di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt The additives used for the emulsion (light-sensitive silver halide coating solution) are as follows. Additives are shown in the amount per mol of silver halide.

1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 mg styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium chloride 50 mg 2 -Anilino-4,6-dimercaptotriazine 60 mg 1,3-dihydroxybenzene-4-ammonium sulfonate 4 g 2-mercaptobenzimidazole-5-sodium sulfonate 1.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1g 1-phenyl-5-mercaptotetrazole 15mg

[0078]

[Chemical 8]

Further, 1.2 g of the dye emulsion dispersion shown below was added to prepare an emulsion coating solution.

Preparation of Dye Emulsion Dispersion The following dyes were dissolved at 55 ° C. in a solvent consisting of 28 l of tricresyl phosphate and 85 l of ethyl acetate. This is called an oil solvent. On the other hand, the following anionic activator (AS) was added to 1.
An aqueous 9.3% gelatin solution containing 35 kg was prepared, and an oil-based solvent and this aqueous solution were placed in a dispersion pot and dispersed while maintaining the liquid temperature at 40 ° C. Phenol and 1,1-dimethylol-1-bromo-1-nitromethane were added to the obtained dispersion liquid in appropriate amounts, and the mixture was made up to 240 Kg with water.

[0081]

[Chemical 9]

Further, exemplary compounds represented by the general formulas [1] and [2] were added to the protective layer liquid as shown in Table 1, and the following were added as additives. The added amount is shown as an amount per 1 l of the 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 (area average particle size 1.2 μm matting agent) 0.5 g Ludox AM (DuPont colloidal silica) 30 mg Glyoxal 40% aqueous solution 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 300 mg

[0084]

[Chemical 10]

As a comparative activator, C ₉ H ₁₉ O-(-CH ₂ CH
₂ O-) ₁₀ H was added to the protective layer as EO as shown in Table 2. The following examination was performed about the obtained sample.

Sensitometry Regarding the obtained sample films No. 1 to 16, a fluorescent intensifying screen SRO-250 (Konica
Sensitometry was carried out by contacting the X-ray from the low-sensitivity surface (B surface) side.

Photographed at a tube voltage of 80 KVP and 20 mA for 0.08 seconds X
A line was irradiated and a sensitometric curve was created by the distance method to determine sensitivity, gamma, and fog. The sensitivity at this time was shown as a relative value when sample No. 1 was set to 100. Furthermore (A
The density of (B side) when the exposure amount is given to give (fog) +1.60 to (side), is obtained by removing the photosensitive layer on the (A side) side with a protease, did.

Incidentally, the development is carried out by an automatic developing machine SRX-502, a developing solution X.
Using D-SR and fixer XF-SR (Konica Corp.), developing temperature 35 ° C, fixing temperature 33 ° C, washing water at 5 ° C / min were supplied at a rate of 5 liters per minute for 45 seconds for the entire treatment process. Processed in mode.

The samples (1 to 16) were exposed to the same light.
The sensitivity of (A side) is obtained by removing the photosensitive layer on the (B side) side with a proteolytic enzyme, and the sensitivity of (B side) is 1 to 16 (B side) with fluorescent intensifying screen SRO-250. , X side under the same conditions from the (A side) side
The sensitivity of (B side) was determined by irradiating a line and removing the photosensitive layer after development (A side). The sensitivity value is calculated as the reciprocal of the X-ray dose required to obtain the density obtained by multiplying the value obtained by subtracting the fog from the maximum density by 0.4, and then adding the fog.
The relative sensitivity is shown when the sensitivity of the A side of o.2 is 100.

Evaluation of Sharpness As the evaluation of the image quality of each sample No. 1 to 16, the sharpness was evaluated by photographing the following Funk chart.

As the fluorescent intensifying screen, SRO-250 (manufactured by Konica Corporation) was used, and the photographing conditions were photographed at a tube voltage of 80 KVP. The treatment was performed in the same manner as in the sensitometry.

The sharpness is the Funk test chart SMS5853.
Exposure (exposure dose) using (sold by Konica Medical Co., Ltd.)
Was exposed to each sample so that the average density of the light and shade produced by the Funk test chart was 0.8 ± 0.02, and the obtained sample was evaluated in the following 5 grades. Sharpness evaluation criteria A: Loupe can identify up to 10LP / mm B: Loupe can identify up to 8LP / mm C: Loupe can identify up to 6LP / mm D: Loupe can identify up to 5LP / mm E: Loupe can identify Evaluation of residual color that can identify up to 4 LP / mm Regarding residual color contamination caused by photosensitive dye, unexposed quadruple film (250 mm x 305 mm) was used as an automatic processor SRX-502, developer XD-SR, and fixer. The film was treated with XF-SR at 35 ° C. for 45 seconds, and then the film was visually evaluated on the light source stand for photographic observation, and the following 5 grades were evaluated.

Evaluation Criteria 5: No Contamination of Residual Color 4: Slight Contamination of Residual Color 3: Slight Contamination of Residual Color but No Practical Problem 2: Slight Contamination of Residual Color but Limitation of Practical Range 1: Contamination of Residual Color Many practically impossible Transportability test Transportability is Konica Auto Feeder AF-1000 (Konica Corporation)
(Manufactured by Mitsui Chemicals Co., Ltd.) was connected to an automatic processor SRX-502, and 500 sheets were continuously conveyed and evaluated according to the following criteria. Evaluation criteria ○: Poor conveyance did not occur △: 1-2 sheets occurred in 500 sheets ×: 3 or more sheets occurred in 500 sheets Sucker mark generation test Reduced due to adsorption and peeling under reduced pressure during automatic conveyance of the film Regarding the presence or absence of sensitized and sensitized sucker marks, the sample film that was unexposed and exposed to a density of 1.0 to 1.3 was processed through an auto feeder connected to an automatic processor, and the degree of sucker marks Was visually evaluated on a photographic observation table.

Evaluation Criteria A: No Sucker Marks At All B: Slightly Slight but No Practical Problems C: Clearly Sucker Marks Present The above test results are shown in the table below. However, Table 1 shows the amounts of emulsion-coated silver on the A side and B side, and the respective sensitivities on the A side and B side. Table 2 shows A-side layer and B
The photographic performance and processability of the sample for comparison and the sample for which the activator of the present invention was added respectively in the protective layer of the surface layer are shown.

[0095]

[Table 1]

[0096]

[Table 2]

As is clear from Table 2, sample N of the present invention
o.6 to 16 had excellent performances in tests such as sharpness, residual color, transportability, and sucker mark, and showed less fog than the comparative sample.

[0098]

According to the present invention, a highly sharp silver halide photographic light-sensitive material having no residual color stain on an image can be obtained. Furthermore, according to the present invention, it is possible to obtain a high-sensitivity silver halide photographic light-sensitive material which can prevent the transportability during film transport and the generation of a vacuum suction cup mark and has less fog.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on both sides of a transparent support, after the light-sensitive material is exposed and developed, the exposure amount is fogging + 1 on one side. When the exposure amount gives a density of .60, the density at the same exposure position on the other surface is fog +0.20 or less, and the surface with the higher density has higher sensitivity than the opposite surface. A photosensitive material which is represented by the following general formula [2] and at least one fluorine-based anionic surfactant represented by the following general formula [1] in the protective layer on the silver halide emulsion layer. A silver halide photographic light-sensitive material, containing at least one of the following fluorine-based cationic surfactants. 2. A method of forming an image by exposing from the high-sensitivity surface side of the light-sensitive material with light having a wavelength of 300 nm or more, which has a latent image forming ability, and developing it to form an image. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the amount of transmitted light reaching the interface between the support and the low-sensitivity emulsion layer is 12% or more and 75% or less of the amount of exposure on the surface of the high-sensitivity surface. In the general formula [1] (Cf)-(Y) _n , Cf is an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y is -COOM, -SO.
₃ M, -OSO ₃ M or -P (= O) (OM) ₂ . M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2. General formula [2] Rf'-L-X ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms,
At least one hydrogen atom is replaced by a fluorine atom. L represents a chemical bond or a divalent group. X ⁺ represents a cation and Z ⁻ represents a counter anion.