JPH095916A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material high in sensitivity and density and small in variation of photographic performance before and after coating owing to the fluctuation of hardness and hardly being scratched even in development processing in an automatic developing machine. CONSTITUTION: The silver halide photographic sensitive material has hydrophilic colloidal layers including alt least one of photosensitive silver halide emulsion layer on a support and when it is immersed in an aqueous solution of 0.375N sodium hydroxide, it takes 5-20min for a binder to begin to dissolve in it, and at least one of the hydrophilic colloidal layers hardened with (1) a compound represented by the general formula in which each of R<1> and R<2> an alkyl group or the like; X is an anion; and (y) is 0 or 1 and a compound having epoxy group; and/or a compound having an aziridine group; and/or a compound having a vinylsulfo group, (2) a total amount of the binder on one side hardened with the hardener represented by the general formula is 2.3-3.0g/m<2> .

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. In particular, it has high sensitivity and high density, has little change in photographic performance after coating due to fluctuations in the degree of hardening, and is a halogenated film that does not easily scratch the film during processing, for example when processed in an automatic processor. The present invention relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, as a binder of a silver halide photographic light-sensitive material, for example, gelatin is generally used as a hydrophilic colloid-forming material, and gelatin is generally used to adjust the degree of swelling of a gelatin layer and increase its mechanical strength. For the purpose, a gelatin hardening method using various compounds is known. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, compounds having a reactive halogen described in US Pat. No. 3,288,755, US Pat.
Aziridine compounds described in U.S. Pat. No. 486, US Pat.
Known are epoxy compounds described in No. 1537, halgencarboxylic aldehydes such as mucochloric acid, dioxane such as dihydroxydioxane and dichlorodioxane, and chromium alum and zirconium sulfate as inorganic hardeners.

However, when these gelatin hardeners are used in photographic light-sensitive materials, they do not have a sufficient hardening action, and the change in the degree of hardening called post-hardening occurs over time due to the slow hardening action on gelatin. There is an adverse effect on the performance of the photographic material (increased fog, decreased sensitivity, etc.), or the coexistence of other photographic additives causes a loss of the hardening effect, or other photographic additives (for example, All of them have some drawbacks, such as ones that reduce the effect of a color former for a color light-sensitive material).

Particularly, the performance variation with time due to post-hardening is a problem for silver halide photographic light-sensitive materials which are required to have a constant and stable image quality (finish of image quality).
In particular, this is a big problem in the medical market where demands are great.

The hardening reaction to gelatin is relatively fast,
As a hardener with little post-hardening, Japanese Patent Publication No. Sho 58-3269.
N-carbamoylpyridinium salts described in JP-B No. 9 and JP-B No. 56-12853 are known, but when these are used, the viscosity of the coating solution increases during the production of a light-sensitive material, and the coating becomes difficult or coating failure occurs. May occur. Furthermore, since the amine compound, which is a by-product after the film hardening reaction, is eluted and accumulated in the developing tank during the developing process to generate an odor, there is a drawback that the working environment is deteriorated.

Further, when it is used as a gelatin hard film for a photographic light-sensitive material having a relatively low hardness, the adhesion between the emulsion layer and the undercoat layer of the base is deteriorated, and during development, especially by an automatic processor. There was a drawback that the emulsion film was easily scratched during the process.

[0007]

The object of the present invention is to solve the above-mentioned drawbacks and to achieve high sensitivity,
A silver halide photographic light-sensitive material that has a high density, has little change in photographic performance after coating due to fluctuations in the hardness, and is less likely to scratch the film during development, especially when processed in an automatic processor. To provide.

[0008]

The above objects of the present invention are as follows.
A silver halide photographic light-sensitive material in which a hydrophilic colloid layer containing at least one light-sensitive silver halide emulsion is formed on a support.
The time when the binder of the light-sensitive material begins to elute when immersed in a sodium hydroxide aqueous solution at 5 ° C for 5 minutes or longer and 20 minutes or less, and at least one hydrophilic colloid layer (for example, any emulsion layer) of the light-sensitive material is used. And / or the other hydrophilic colloid layer) is hardened with a compound represented by the general formula (1) and a compound having an epoxy group and / or a compound having an aziridine group and / or a compound having a vinyl sulfone group. It has been found that this can be achieved by the characteristic silver halide photographic light-sensitive material. (The general formula (1) will be described later in detail.)

The above object of the present invention is to provide a silver halide photographic light-sensitive material in which a hydrophilic colloid layer containing at least one light-sensitive silver halide emulsion layer is formed on a support. The time for which the binder of the light-sensitive material begins to elute when immersed in a 375 N aqueous solution of sodium hydroxide at 50 ° C. is 5 minutes or more and 20 minutes or less, and at least one hydrophilic colloid layer (emulsion layer) of the light-sensitive material. And / or other hydrophilic colloid layer) is hardened with a compound represented by the general formula (1) (described later), and the total amount of the hydrophilic binder present on one side of the support of the photosensitive material is 2.3 g / m ² per unit area
It was found to be achieved by a silver halide photographic light-sensitive material characterized by being 3.0 g / m ² or less.

The present invention will be described in more detail below. First, the compound represented by formula (1) according to the present invention will be described.

General formula (1)

Embedded image

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group or alkoxy group which may have a substituent, and R ² represents an alkyl group which may have a substituent, an acyl group or an acylamino group. Represents a group, X represents an anion, y is 1 or 2, and when y is 1, an internal salt is formed.

In the general formula (1), it is a preferred embodiment that R ² is an alkylene sulfonic acid or an acylamino group.

R ² in the general formula (1) is, for example,-(-C
_{H 2 -) m-SO 3} -, -NR 3 COR 4, - (- CH
^{_{2 -) p-CONR 7 R}} 8, - (- CH 2 -) q-NR
⁹ R ¹⁰ ,-(-CH _2- ) s-CH- (LR ¹² ) -R ¹¹
Can be Here, R ³ represents a hydrogen atom or an alkyl group which may have a substituent, and R ⁴ represents an alkyl group which may have a substituent, an alkoxy group, —O — (— C
_{H 2 -) n-SO 3} -, -NR 5 R 6, - (- CH
₂₋ ) n—SO ₃ ^— , R ⁵ and R ⁶ are a hydrogen atom or an alkyl group which may have a substituent, — (— CH ₂ —)
n-SO ₃ ^- represents, R ⁷ represents an alkyl group or an aryl group which may have a hydrogen atom or a substituent, R ⁷ is a hydrogen atom or an optionally substituted alkyl group or an aryl group Represents a group forming a 5- or 6-membered aliphatic ring with R ⁷ , R ⁹ represents a hydrogen atom or an alkyl group which may have a substituent, or —COR ⁴ , and R ¹⁰ represents a hydrogen atom or a substituent. An alkyl group which may have a group or-
(—CH ₂ —) r—SO ₃ ^— , L is —O—, —N
R ¹³ - represents, R ¹¹ represents an alkyl group which may have a hydrogen atom or a substituent, R ¹² represents an alkyl group which may have a hydrogen atom or a substituent, -COR ^14, -CONHR ¹⁵
Represents, R ¹³ represents, R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or an alkyl group which may have a substituent, and m is 0, 2
-4, n is 1-3, p is 0-2, q and r are 1-3, s
Represents 2 to 3.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group or an alkoxy group which may have a substituent, and R ² represents-(-CH _2- ) m.
It is preferable to take an embodiment which is —SO ₃ ^— or —NR ³ COR ⁴ .

The compounds that can be used in the present invention are exemplified below. However, the present invention is not limited to these.

[0017]

Embedded image

[0018]

Embedded image

[0019]

[Chemical 6]

[0020]

[Chemical 7]

These compounds can be easily synthesized by the methods described in the literature. For example, as a document, "Che
m. Ber. 40, 1831 (1907) "and
"J. Phys. Chem. 68: 3149".

Next, the compound having an epoxy group which can be used in the present invention will be described. In the present invention, any compound having an epoxy group and exhibiting a hardening effect can be arbitrarily used, but in the practice of the present invention, the following specific compounds can be preferably used.

Specific Example Compound

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

[Chemical 12]

Most of the above compounds are commercially available,
It is easily available. The addition method of the compound having an epoxy group may be such that the compound is dissolved in water or an organic solvent such as alcohol or acetone and then added as it is, or an interface such as dodecylbenzene sulfonate or nonylphenoxyalkylene oxide. It may be added after being dispersed using an activator. The preferred amount is
It is 1 to 1000 mg / m ² .

Next, the compound having an aziridine group which can be used in the present invention will be described. In the present invention, any compound having an aziridine group and exhibiting a hardening effect can be arbitrarily used, but in the practice of the present invention, the following specific compounds can be preferably used.

[0030]

Embedded image

Next, the compound having a vinyl sulfone group which can be used in the present invention will be described. In the present invention, any compound having a vinyl sulfone group and exhibiting a hardening effect can be arbitrarily used, but in the practice of the present invention, the following specific compounds can be preferably used.

[0032]

Embedded image

[0033]

Embedded image

The silver halide photographic light-sensitive material of the present invention has a time in which the binder of the light-sensitive material begins to elute when the light-sensitive material is dipped in a 0.375 N aqueous solution of sodium hydroxide at 50 ° C. for 5 minutes to 20 minutes. However, in this case, the time when the binder starts to elute (called the melting time) is measured by the following method.

A light-sensitive material cut into a size of 1 cm × 2 cm is sandwiched by clips, and left still in a beaker at 50 ° C. in an aqueous solution of 0.375 N sodium hydroxide.
When measuring the elution time, the sodium hydroxide aqueous solution is not stirred. The measurement range of the elution time is such that the temperature of the aqueous sodium hydroxide solution is maintained at 50 ° C ± 0.5 ° C.

Depending on the time when the binder is eluted from the light-sensitive material (film), or depending on the light-sensitive material, the emulsion layer may be peeled from the support before the binder is eluted. The shorter time is defined as the time when the elution of the present invention begins.

Next, the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention and the silver halide grains in the emulsion will be described. The average grain size of the silver halide grains used in the present invention is arbitrary, but is preferably 0.1 to 2.0 μm, particularly preferably 0.4 to 1.4 μm.

The grain size of the silver halide grains is defined here as the diameter of a sphere having a volume equal to that of the grains from the observation of an electron micrograph of the 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 size of the silver halide grains can be controlled by the temperature at the time of grain formation and the addition rate of the silver salt and halide aqueous solution. The grains may be grown 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, silver iodide, silver iodobromide, silver bromide, silver chlorobromide,
It can be supplied in combination of silver chloride, a solution containing a halogen ion, a solution containing a silver ion, and the like.

As the silver halide emulsion of the present invention, those which are monodisperse are preferably used, and the variation coefficient of the average grain size is 25.
%, More preferably 20% or less.

The silver halide composition of the silver halide emulsion of the present invention is arbitrary. Silver iodobromide and silver chloroiodobromide are preferably used, but the silver iodide content is preferably 1.5 mol%.
The above is more preferable, and silver iodobromide having a silver iodide content of 2 mol% or more is more preferable.

In the present invention, so-called core-shell type grains having a high iodine layer inside can be used as the silver halide grains. In this case, the iodide content of the internal high-iodity layer is preferably 25 mol% or more, more preferably 30 mol% or more.

The layer located outside the high iodine layer may be of any silver halide composition as long as it has a lower iodine content than the high iodine layer, but the iodine content is preferably 0.5 mol. % Or less, and more preferably pure silver bromide.

For the core / shell type particles, see Japanese Patent Laid-Open No.
Such silver halide grains can be prepared by the methods described in JP-A No. 9-177535, JP-A No. 59-178447, JP-A No. 60-35772, JP-A No. 60-147727 and the like.

In order to remove soluble salts, the emulsion may be subjected to a water washing method such as a Nudel water washing method and a flocculation sedimentation method. As a preferable washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B No. 35-16086, or JP-A-Sho 6
Agglomerated polymer agent exemplified G3 and G8 described in JP-A-3-158644
And the like. Particularly preferred is a desalting method.

The emulsion can be chemically sensitized. The chemical sensitization methods include so-called sulfur sensitization, gold sensitization and periodic table V.
Sensitization with Group III noble metals (eg, Pd, Pt, Id, etc.) and combinations thereof can be used. Among them, a combination of gold compound, sulfur compound and Se compound is preferable. The addition of the Se compound can be arbitrarily set, but is preferably used together with sodium thiosulfate during chemical sensitization. More preferably Se
It is preferable to use the compound and sodium thiosulfate in a molar ratio of 1: 1 or less, more preferably 1: 2 or less. It is also preferable to carry out in combination with reduction sensitization.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. Particularly preferable compounds are azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having these mercapto groups and compounds having a benzene ring.

It is also a preferred embodiment to use a cyanine dye of monomethine or trimethine.

The silver halide according to the present invention can be subjected to a reduction treatment, so-called reduction sensitization method. As the reduction treatment, a method of adding a reducing compound, a method called p.
It may be applied to the silver halide emulsion by a method of passing a silver ion excess state of Ag = 1 to 7, a method of passing a high pH state of pH = 8 to 11 called high pH ripening, and the like. Also, 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, sulfite. Examples thereof include salts and the like, and particularly preferable are thiourea dioxide, silver stannous chloride, and dimethylamine borane. The addition amount of the reducing compound is reducible and the type of silver halide of the compound varies depending emulsion preparation conditions such as dissolving conditions, preferably per mole of silver halide ^{1 × 10 - 8 ~1 × 10} - A range of ² moles is suitable. These reducing compounds are preferably dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

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, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugars such as sodium alginate, dextran and starch derivatives. Various synthetic hydrophilic polymer substances such as derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, 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 5,000 to 100,000 together with gelatin. Examples of these are, for example, JP-A-1-307738 and 2625.
32, 224748, 24445, 166
031, JP-A-64-65540, JP-A-63-10.
No. 1841 and No. 153538.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo, Japan
an. No. In addition to oxygen-treated gelatin as described on pages 16, 30 (1966), gelatin derivatives (eg gelatin include acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinyl sulfonamides, malein). Those obtained by reacting various compounds such as imide compounds, polyalkylene oxides, and epoxy compounds) are included.

The emulsion used in 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
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month). The types of compounds shown in these three Research Disclosures and their locations 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 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant 26 to 7 XI 650 right 1005-6 XI antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII slippery agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 26 XXII 1003

The photographic processing of the light-sensitive material of the present invention is carried out, for example, in RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to XXI, 1011 to 10.
The treatment with the treatment liquid as described on page 12 can be performed. This process may be a black and white photographic process for forming a silver image. The treatment temperature is usually preferably 18-5.
It is processed in the range of 0 ° C.

As developers in black and white photographic processing, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone),
Aminophenols (for example, N-methyl-p-aminophenol) and the like can be used alone or in combination. It should be noted that known well-known preservatives, alkaline agents, pH buffers, antifoggants, development accelerators, surfactants, defoamers, color tones, water softeners, solubilizers, viscosity imparting agents are known for the developer. Etc. can be used as needed.

A fixing agent such as thiosulfate or thiocyanate is generally used in the fixing solution, and water-soluble aluminum 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.

[0059]

EXAMPLES Examples of the present invention will be described below. still,
Naturally, the invention is not limited to the examples described below.

Example 1 (Preparation of seed particles) The Ag ionic liquid and the halide ionic liquid (the ratio of Br ion to I ion was 98: 2 by the double jet method while maintaining 60 ° C., pAg = 8 and pH = 2. ) Was added to obtain a monodispersed silver iodobromide emulsion having an average grain size of 3.0 μm and a silver iodide content of 2 mol%. The pH of the obtained emulsion was adjusted to 6 with sodium carbonate, followed by precipitation using a demol aqueous solution and a magnesium sulfate aqueous solution manufactured by Kao Atlas Co., and decantation to remove unnecessary inorganic salts.

When the grains of the resulting emulsion were observed by an electron microscope, the twin generation rate was 1% or less.

(Preparation of grown grains) 0.033 mol of the above-prepared seed emulsion in terms of mol of Ag was added to the following A1 solution kept at 70 ° C., and 5 minutes after the addition, the following B1 and C were added.
One solution was added by the double jet method. The addition rate was such that the B1 and C1 solutions were added in equal amounts, respectively, within the range where no new nuclei were generated.

At this time, a separately prepared 56% acetic acid solution was added as needed so that the pH was kept at 7. Separately prepared as necessary to keep the potential at 70 mV 2
A 5% potassium bromide aqueous solution was appropriately added.

Immediately after addition to the B1 and B2 solutions, B2 and C
The two solutions were added in the same manner as the B1 and C1 solutions. However, the addition rate of the B2 solution was 1.26 times that of the C2 solution. The pH was kept at 7 and the potential was kept at 70 mV during the addition.

When 70% of the added amount of the B2 solution was added, the total amount of the D1 solution was added. The potential after this was not adjusted with a separately prepared potassium bromide aqueous solution, and the particles were grown as they were. [A1] Ossein gelatin 15.9 g Copolymer of polypropyleneoxy and polyethyleneoxy (block polymer) MW = 1500 (10% methanol solution) 0.14 ml 28% ammonia water 17.5 ml 56% acetic acid 26.0 ml Adjust to 142.0 ml with water [B1] Silver nitrate 16.6 g 28% ammonia water 13.0 ml Adjust to 57.4 ml with water [C1] Ocein gelatin 0.28 g Potassium bromide 8.1 g Potassium iodide 4 0.87 g Water to 57.4 ml [B2] Silver nitrate 147.7 g 28% ammonia water 115.7 ml Water to 248.5 ml [C2] Ocein gelatin 1.00 g Potassium bromide 100.3 g Water 198.3 mm To 70 milliliters and torr [D1] Potassium bromide 44.2g Water

After the addition of the B2 and C2 solutions was completed, the pH was adjusted to 6 with a 56% acetic acid solution. The obtained emulsion was precipitated using a demol aqueous solution and a magnesium sulfate aqueous solution manufactured by Kao Atlas Co., and decantation was performed to remove unnecessary inorganic salts, gelatin was added, and the emulsion was dispersed again.

The emulsion has a potential of 50 mV at 50 ° C., p
H was 5.85. When 200 particles thus obtained were arbitrarily selected and the particle size was measured by an electron microscope, the average particle size was 1.0 μm and the coefficient of variation of the particle size was 0.15.

1 mol per mol of silver was added to the emulsion prepared above.
% NH ₄ SCN; 8.0 cc, 0.2% HAuCl ₄ ;
0.17 cc, 0.25% Na ₂ S ₂ O ₃ ; 0.6c
c, a chemical sensitizer consisting of 0.36 mg of a triphenylphosphine selenide gelatin dispersion of needle-shaped crystals of triphenylphosphine selenide having an average major axis length of 10 μm was added. However, immediately before the addition, the following spectral sensitizing dye was added and chemically aged at 48 ° C.

At the time when the fog rise becomes 0.02,
The following spectral sensitizing dye was added again, and 4-hydroxy-6-
2.8 g of methyl-1,3,3a, 7-tetrazaindene was added per mol of silver halide, and the temperature was lowered to stop the chemical ripening.

Embedded image

Similarly, particles having an average particle size of 0.7 μm and 1.3 μm were prepared and chemically sensitized. Chemical sensitizers, sensitizing dyes, 4-hydroxy-1,3,3a,
7-Tetrazaindene was added in an amount proportional to the surface area of the particles.

The emulsions prepared as described above were mixed at the following ratio (per amount of silver), and then the following compounds and compounds shown in Table 1 were added per mol of silver to prepare emulsion coating solutions. .

Mixing ratio of emulsion 1.3 μm: 1.06 μm: 0.7 μm = 8: 50: 42 Additive compound 1-phenyl-5-mercaptotetrazole 17 mg 1-trimethylolpropane 8 g t-butyl-catechol 80 mg polyvinylpyrrolidone ( Molecular weight 10,000) 850 mg Styrene-maleic anhydride copolymer 2.0 g Nitrophenyl-triphenyl-phosphonium chloride 16 mg 1,3-Dihydroxybenzene-4-ammonium ammonium sulfonate 4.0 g 1,1 dimethylol-1-bromo- 1-nitromethane 6.2 mg nC ₄ H ₉ CH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1400 mg

[0073]

Embedded image

The additives used in the emulsion protective layer liquid are as follows. The amount of addition is shown in an 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

[0075]

Embedded image Regarding the compound represented by the general formula (1) and the hardener,
It is described in Table 1.

[0076]

[Table 1]

The emulsion coating solution and the emulsion protective film solution prepared as described above using the various compounds shown in Table 1 were simultaneously coated on both sides of the above-mentioned undercoated base, and sample No.
1-34 were obtained.

The amount of silver in the emulsion layer was 2.8 per side.
g / m ^2, gelatin with the amount of emulsion layer 2.4 g / m ^2, the protective film is 1.3 g / m ^2.

The obtained sample was left in an environment of 25 ° C. and 40% pH for 12 hours and a sample left for 1 month.
The sensitivity, maximum density (Dm), and ease of scratching in the developing solution were evaluated.

The sensitivity of the sample was measured by Konica Corporation NR160.
X-ray exposure was performed using an aluminum step wedge, and the result was evaluated as the reciprocal of the exposure amount that gives fog + density 1.0.

The susceptibility of the film to scratches in the developing solution was determined by immersing the photosensitive material in the following developing solution for 40 seconds, placing the film on a smooth surface, and applying a weight with a stainless nail having a width of about 3 mm. The scratches that were formed when the film was scratched by changing the value were sensory evaluated. Level 5 represents a level at which no scratches occur, and level 3 represents a limit level acceptable in the market.

The processing was carried out under the following developing solution, fixing solution and processing conditions. Developer Part-A Potassium hydroxide 310g Potassium sulfite (50% solution) 1950g Diethylenetetraamine pentaacetic acid 90g Sodium hydrogencarbonate 108g 5-Methylbenzotriazole 1.6g 1-Phenyl-5-mercaptotetrazole 160mg Hydroquinone 290g Water was added. Make up to 3000 ml. Part-B glacial acetic acid 158 g triethylene glycol 150 g 1-phenyl-3-pyrazolidone 19.5 g 5-nitroindazole 0.32 g N-acetyl-D, L-penicillamine 1.1 g Water is added to make 350 ml. Part-A and B were mixed and made up to 10.8 liters with water. Starter (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 Add water 1.0 Finish to liters. The amount of starter added was 20 cc per liter of the developer. Fixer Part-A Ammonium thiosulfate (70 wt / vol%) 4600 g Sodium sulfite 150 g Sodium acetate trihydrate 340 g Sodium citrate 40 g Gluconic acid 60 g Boric acid 28 g Glacial acetic acid 120 g Water is added to make 4000 ml. Part-B Aluminum sulphate 56 g Sulfuric acid (50 wt%) 90 g Water is added to make 700 ml. Mix Part-A and Part-B and mix with water for 16.4.
Finished to liters. Using the above developer and fixer,
The film is processed under the following processing conditions. Processing step Processing temperature (° C) Processing time (sec) Insertion --- 2.4 Development + crossover 35 29.4 Fixing + crossover 33 21.8 Washing + crossover 18 13.0 Squeeze 40 9.0 Dry 50 14.4 Total --90.0

The obtained results are shown in Table 2. From Table 2, the silver halide photographic light-sensitive material according to the present invention has high sensitivity and high density, and the variation in coating of these performances is small,
In addition, it has the effect of high resistance to roller marks and scratches.

[0084]

[Table 2] * 1: Performance difference between the sample 12 hours after application and the sample 1 month after application MT: Melting time, that is, when the sample is immersed in 0.375N 50 ° C sodium hydroxide aqueous solution, the binder of the sample elutes. Time to start

Example 2 Sample No. 1 in Example 1 was used. When 18 was prepared, the amount of gelatin in the emulsion layer and the protective layer was set to the amount shown in Table 3. Otherwise, in the same manner as in Example 1, Sample No. 35-39 were created.

The results obtained are shown in Table 3. From Table 3, the total amount of hydrophilic binders on one side is 2.3 to 3.0 g / m ^2.
It can be seen that the silver halide photographic light-sensitive material has high sensitivity and high density, has less variation in coating of these performances, has high roller mark resistance, and is hard to be scratched.

[0087]

[Table 3]

[0088]

As described above, according to the present invention, high sensitivity, high density, and little change in photographic performance after coating due to fluctuations in the degree of hardening, and during development processing, especially in an automatic developing machine It was possible to provide a silver halide photographic light-sensitive material that is less likely to have a film scratch or a roller mark when processed.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material in which a hydrophilic colloid layer containing at least one light-sensitive silver halide emulsion layer is formed on a support, wherein the light-sensitive material is hydroxylated at 0.375 N at 50 ° C. The time when the binder of the photosensitive material begins to elute when immersed in an aqueous sodium solution is 5 minutes or more and 20 minutes or less, and at least one hydrophilic colloid layer of the photosensitive material is represented by the following general formula (1). And a compound having an epoxy group and / or a compound having an aziridine group and / or a compound having a vinyl sulfone group. General formula (1) In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group or alkoxy group which may have a substituent, and R ² represents an alkyl group which may have a substituent, an acyl group or an acylamino group. , X represents an anion, y is 1 or 2, and when y is 1, an intramolecular salt is formed. 2. A silver halide photographic light-sensitive material in which a hydrophilic colloid layer containing at least one light-sensitive silver halide emulsion layer is formed on a support, wherein the light-sensitive material is hydroxylated at 0.375 N at 50 ° C. The time when the binder of the photosensitive material begins to elute when immersed in an aqueous sodium solution is 5 minutes or more and 20 minutes or less, and at least one hydrophilic colloid layer of the photosensitive material is represented by the following general formula (1). And a total amount of hydrophilic binders present on one side of the support of the photosensitive material is 2.3 g / m ² or more and 3.0 or more per unit area.
A silver halide photographic light-sensitive material characterized by having a content of g / m ² or less. General formula (1)