JPH10171061A - Sliver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material superior in graininess, silver color tone, and pacification resistance, and capable of performing ultrahigh-speed processing, by incorporating a leuco dye to impart a blue dye by reaction with the oxidant of a developing agent in a hydrophilic colloidal layer and a specified compound in a transparent support. SOLUTION: The silver halide photographic sensitive material is provided on at least one side of the transparent support with the hydrophilic colloidal layers including at least one photosensitive silver halide emulsion layer, and the hydrophilic colloidal layer contains the leuco dye to impart the blue dye by reaction with the oxidant of the developing agent, and the transparent support is a biaxially stretched film-forming polyester film composed substantially of polyethylene 2,6-naphthalene obtained by copolymerizing naphthalenedicarboxylic acid as a dicarboxylic acid component and ethylene glycol as a diol component.

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 which is excellent in graininess, silveriness and devitrification and can be processed very quickly.

[0002]

2. Description of the Related Art In recent years, advances in electronics have dramatically shortened access times to images, and silver halide photographic light-sensitive materials are required to be processed more and more rapidly. For this reason, silver halide photographic light-sensitive materials are increasingly required to have various physical properties, and one of such demanding performances is graininess and silver color.

With the rapid processing in an automatic processor, the tabular silver particles employed for high sensitivity by reducing the amount of silver and the silver color tone deteriorate with a yellow tint due to the rapid processing. Is also a problem.

[0004] In addition, a matting agent or the like may be added to reduce friction during high-speed conveyance, but devitrification may be deteriorated, and it is becoming difficult to satisfy both performances.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in graininess, silveriness and devitrification and can be processed very quickly.

[0006]

[Means for Solving the Problems]

(1) In a silver halide photographic light-sensitive material having at least one hydrophilic silver colloid layer containing at least one photosensitive silver halide emulsion layer on at least one side of a transparent support, the hydrophilic colloid layer contains a developing agent. Halogenation, comprising a biaxially stretched polyester film containing a leuco dye which reacts with an oxidant to give a blue dye, and wherein said transparent support is substantially a polyethylene-2,6-naphthalate-containing polyester film. Silver photographic photosensitive material.

(2) In a silver halide photographic material having a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer on at least one side of a transparent support, a photosensitive silver halide emulsion A non-photosensitive hydrophilic colloid layer containing oil between the layer and the top layer, and the transparent support is a biaxially oriented polyester film substantially containing polyethylene-2,6-naphthalate A silver halide photographic light-sensitive material comprising:

Hereinafter, the present invention will be described in detail.

The polyester constituting the biaxially stretched polyester film of the present invention is polyethylene-2,6-naphthalate. This is a film-forming polyester obtained by copolymerizing naphthalenedicarboxylic acid as a dicarboxylic acid component and ethylene glycol as a diol component.

The polyester of the present invention can be used not only by the above-mentioned polyester comprising polyethylene-2,6-naphthalate, but also by mixing with other polyesters. Even in that case, it is preferable that the content of polyethylene-2,6-naphthalate is 40 mol% or more of the whole.

The dicarboxylic acid components constituting other polyesters include 2,6-naphthalenedicarboxylic acid and 2,2-naphthalenedicarboxylic acid.
7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketonedicarboxylic acid, phenylindanedicarboxylic acid Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexane dimethanol, and the like.
2,2-bis (4-hydroxyphenyl) propane,
Examples thereof include 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol.

Among the polyesters containing these as main constituents, terephthalic acid and 2,2 are used as other dicarboxylic acid components in view of transparency, mechanical strength, dimensional stability and the like.
6-Naphthalenedicarboxylic acid, polyesters containing ethylene glycol and 1,4-cyclohexanedimethanol as major components as diol components are preferred. Among them, polyethylene-2,6-naphthalate, a copolymerized polyester composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and a polyester having a main component of a mixture of two or more of these polyesters are preferred. .

The polyester of the present invention may contain an antioxidant. In particular, the effect is remarkable when the polyester contains a compound having a polyoxyalkylene group. The type of the antioxidant to be contained is not particularly limited, and various antioxidants can be used. Examples thereof include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds. Can be. Above all, an antioxidant of a hindered phenol compound is preferable in terms of transparency.

The content of the antioxidant is usually from 0.01 to 2% by weight, preferably from 0.1 to 2% by weight, based on the polyester.
0.5%. By setting the content of the antioxidant in this range, it is possible to prevent the so-called fogging phenomenon in which the density of the unexposed portion of the photographic light-sensitive material is increased, and the haze of the film can be suppressed to be low, so that a photograph having excellent transparency can be obtained. Support is obtained. In addition, these antioxidants may be used alone or in combination of two or more.

The polyester of the present invention may be provided with lubricity as required. The means for imparting lubricity is not particularly limited, but a method of adding external particles for adding inert inorganic particles to the polyester, a method for depositing internal particles for depositing a catalyst to be added at the time of synthesis of the polyester, or a method such as a surfactant is used. A method of applying the composition to the surface is generally used. Among these, an internal particle precipitation method that can control the particles to be deposited relatively small is preferable because lubricity can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but it is particularly preferable to use Ca and Mn because high transparency can be obtained. One of these catalysts may be used, or two or more of them may be used in combination.

The method for synthesizing the polyester as a raw material for the polyester of the present invention is not particularly limited, and it can be produced according to a conventionally known polyester production method. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first using a dialkyl ester as a dicarboxylic acid component, a transesterification reaction between the dicarboxylic acid component and a diol component, and heating this under reduced pressure. A transesterification method in which polymerization is performed by removing an excess diol component can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. In addition, in each process during the synthesis, a coloring inhibitor, an antioxidant, a crystal nucleating agent, a slipping agent, a stabilizer, an antiblocking agent, an ultraviolet absorber, a viscosity modifier, an antifoaming agent, a clarifying agent, an antistatic agent, pH adjuster,
Dyes, pigments and the like may be added.

The thickness of the polyester of the present invention is not particularly limited. What is necessary is just to set so that it may have required intensity | strength according to the use purpose.

Further, when used for medical or printing photographic light-sensitive materials, 50 to 300 μm, particularly 80 to 200 μm
It is preferred that If the thickness is less than this range, the required strength may not be obtained, and if the thickness is too large, the curl will be larger.

Further, the polyester of the present invention preferably has a haze of 3% or less. More preferably, it is 1% or less. When the haze is more than 3%, when the film is used as a support for a photographic light-sensitive material, an image is blurred and becomes unclear. The haze is ASTM-D1003-
52 was measured in accordance with No. 52.

The Tg of the polyester of the present invention is preferably 60 ° C. or higher. Tg is determined as an average value of a temperature measured by a differential scanning calorimeter at which a baseline starts to be shifted and a temperature at which the baseline returns to a new baseline. When the Tg is at least this value, a photosensitive material having no deformation of the film in the drying step of the developing machine and having a small curl after development can be obtained.

Next, a method for producing the polyester film of the present invention will be described.

A method for obtaining an unstretched sheet and a method for uniaxially stretching in the longitudinal direction can be performed by a conventionally known method.
For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled, solidified, and unstretched Get a sheet. Then, the obtained unstretched sheet is heated in a range from the glass transition temperature (Tg) of the polyester to Tg + 100 ° C. through a plurality of roll groups and / or a heating device such as an infrared heater, and subjected to single-stage or multi-stage longitudinal stretching. It is. The stretching ratio is usually in the range of 2.5 to 6 times, and it is necessary to make the subsequent transverse stretching possible. When the sheet has a multilayer structure, the setting of the stretching temperature is preferably based on the highest Tg of the Tg of the polyester of each constituent layer.

At this time, when the polyester is laminated,
A conventionally known method may be used. For example, a plurality of extruders and a co-extrusion method using a feed block type die or a multi-manifold type die, melt extrusion of a single layer film constituting a laminated body or other resin constituting a laminated body on a laminated film from an extruder, and cooling. Examples thereof include an extrusion lamination method of cooling and solidifying on a drum, and a dry lamination method of laminating a single-layer film or a laminated film constituting a laminate via an anchor agent or an adhesive as necessary. Among them, a co-extrusion method that requires a small number of production steps and has good adhesion between the layers is preferable.

Next, the polyester film uniaxially stretched in the machine direction obtained as described above was subjected to Tg to Tm-2.
In a temperature range of 0 ° C., the film is stretched in the transverse direction and then heat-set. The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is determined by measuring the physical properties of the obtained biaxially stretched film and appropriately adjusting the film to have preferable characteristics. In the case of the present invention, the elastic modulus in the width direction is made larger than the elastic modulus in the longitudinal direction. It may be changed according to the purpose of use. At this time, the temperature difference in the stretched region divided into two or more is 1 to 50.
It is preferable to perform transverse stretching while sequentially increasing the temperature in the range of ° C. because the fluctuation distribution of physical properties in the width direction can be reduced. Further, after the transverse stretching, the film is preferably kept at a temperature not higher than the final transverse stretching temperature and at a temperature of not less than Tg-40 ° C for 0.01 to 5 minutes, because the distribution of physical properties in the width direction can be further reduced.

The heat fixing is carried out at a temperature higher than the final transverse stretching temperature and within a temperature range of Tm-20 ° C. or lower, usually 0.5 to 30 ° C.
Heat set for 0 seconds. At this time, it is preferable to heat-set while sequentially increasing the temperature in a range of 1 to 100 ° C. in the two or more divided regions.

The heat-fixed film is usually cooled to Tg or less, cut off the clip holding portions at both ends of the film, and wound up. At this time, within the temperature range of not more than the final heat-setting temperature and not less than Tg, 0.1 to 0.1 in the width direction and / or the longitudinal direction.
It is preferable to perform a 10% relaxation treatment. Further, it is preferable that the cooling is gradually performed from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. The means for cooling and relaxing treatment is not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film.
The cooling rate is a value determined by (T1−Tg) / t, where T1 is the final heat setting temperature and t is the time required for the film to reach Tg from the final heat setting temperature.

Since the most optimal conditions for the heat setting, cooling, and relaxation treatments differ depending on the polyester constituting the film, the physical properties of the obtained biaxially stretched film are measured and adjusted appropriately so as to have preferable characteristics. It may be determined by doing so.

In the production of the film, a functional layer such as an antistatic layer, a lubricating layer, an adhesive layer and a barrier layer may be applied before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be performed as necessary. Further, for the purpose of improving the strength, stretching used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal-horizontal stretching, and horizontal / longitudinal stretching can be performed.
Of course, the clip gripping portions at both ends of the cut film are crushed, or after granulation, depolymerization, repolymerization, etc., if necessary, as raw materials for the same type of film or different types May be reused as a film raw material.

The biaxially stretched polyester film obtained as described above becomes difficult to wind over time. This is because the amorphous portion of the polyester starts to aggregate for a long time in spite of the Tg or less to form a fibril-like ribbon which is a spherulite component (PH Gel).
et al. J. Macromol. Sci. Phys
s. , B1, 235, 251 (1967)). When this phenomenon is measured by DSC in the following manner, it is observed that the endothermic peak not observed immediately after the film formation increases with the standing time, and the winding becomes harder with the size. In this case, if the temperature is equal to or lower than Tg, the same effect can be obtained even if the processing time is shortened as the temperature is increased, and the peak top of the endothermic peak shifts to the high temperature side with the processing temperature.

However, in this case, if a temperature higher than the temperature at which the film is left, particularly higher than Tg, is applied, the molecules in the amorphous portion start to move, so that the microfibrils are broken, and the state returns to a state in which the microfibrils are easily wound. .

As a method for obtaining the same effect, the film is subjected to a heat treatment at a temperature higher than Tg.

<Glass transition temperature Tg> 10 mg film
Is melted at 300 ° C. in a nitrogen flow of 300 cc per minute,
Immediately quench in liquid nitrogen. The quenched sample is set on a differential scanning calorimeter (DSC8230, manufactured by Rigaku Denki Co., Ltd.), and the temperature is raised at a rate of 10 ° C./min in a nitrogen flow of 100 cc / min to detect Tg and Tc. Tg is a temperature of an average value of a temperature at which the baseline starts to be biased and a temperature at which the baseline returns to a new one. Note that the measurement start temperature is a temperature lower than the measured Tg by 50 ° C. or more.

If the heat treatment temperature is low, it takes a very long time to obtain the effect of reducing curling and curling, making it difficult to manufacture continuously, resulting in poor productivity. If the heat treatment temperature is high, the curling reduction effect cannot be obtained.

A more preferable range is Tg + 5 ° C. or higher, and Tg
+ 25 ° C or lower. When the film has a multilayer structure, the highest Tg among the polyesters constituting the layer substantially responsible for the rigidity of the film is used as a reference.

The heat treatment time may be any time sufficient for heating the film, and is usually at least 0.01 minute.
Further, the effect of reducing the curl caused by such heat treatment is saturated in about 6 minutes. In order to further accelerate the effect, it is preferable to perform a heat treatment at 130 ° C. ± 20 ° C. for 0.01 to 30 minutes. From the viewpoint of continuous production, the shorter the heat treatment time, the better.
Less than a minute is more preferred.

The method of performing the heat treatment of the present invention is not particularly limited. However, the present invention is characterized in that the heat treatment can be performed in a much shorter time than the conventional curl reduction method to obtain the curl reduction effect. For example, even if the film is heat-treated in a state where the films are stacked or rolled, the effect of the present invention is hardly obtained because the film is not uniformly heated. Therefore, a method that can uniformly heat the film in a short time is preferable. As such a method, for example, the film is continuously transported by gripping the both ends of the film with pins or clips, or transporting the roll by a plurality of rolls or air transport that blows air onto the film and floats the film. Heat treatment by spraying heated air from one or more slits on one or both sides of the film surface, using radiant heat from an infrared heater, or contacting with a plurality of heated rolls. Method.

Further, since the heat treatment temperature is equal to or higher than the Tg of the film, if the heat treatment is performed in a state where the film is wound in one direction, a habit of the wound state is formed. Therefore, it is preferable to perform the heat treatment while maintaining the film in a flat state. However, if necessary, the film is brought into contact with the film so that the curl balance with the photographic emulsion layer can be obtained when the photographic material is finally formed. It is also possible to adjust the diameter of the heat roll or the like, or to make it pass through an appropriate curved surface by air conveyance, thereby giving a proper winding state.

The method of keeping the film flat is as follows.
Although there is no particular limitation, for example, the above-described pin and clip transfer method, air transfer method, roll transfer method, and the like can be used. The roll transport method is not perfectly flat because the roll is transported with a wrap angle with the film, but
Since the film is alternately contacted with the roll on the front and back, and the winding direction of the film does not become one direction, the film can be regarded as substantially flat.

The step of applying the heat treatment as described above may be any step from the production of the film to the cutting and packaging of the final product.
Thereafter, if the film is heated at a temperature higher than the Tg for 30 minutes or more, the effect is reduced. In particular, care must be taken when the temperature is equal to or higher than Tc, since the effect disappears in a very short time. Of course, even if the effect is once lost, the effect of reducing the original curl can be obtained by performing the heat treatment again.

The heat treatment may be performed in one stage, or may be performed in two or more zones with a temperature difference. Slow cooling may be performed. Also, an adhesive layer, a conductive layer,
After applying and drying various functional layers (so-called undercoat layers) such as a slippery layer and a magnetic recording layer, it is preferable to subsequently perform heat treatment.

Also in this case, the heat treatment can be performed by adjusting the drying temperature or by adding necessary heating equipment, and it is not necessary to newly install a transfer equipment. The heat treatment may be performed in one stage, or may be performed in two or more zones with a temperature difference.

The heat-treated base thus obtained is
Since it is higher than Tg, it needs to be cooled to room temperature. The cooling at this time is preferably as fast as possible in order to obtain flatness, and is preferably at least -1 ° C / min or more.

The film heat-treated as described above and cooled to room temperature is wound up and stored until it is sent to the next step. At this time, the moisture content of the film was set to 0.1
% Is preferable because curling here can be prevented. The moisture content of the film is a value determined by measuring the film at a drying temperature of 150 ° C. using a trace moisture meter (for example, CA-05 manufactured by Mitsubishi Kasei Corporation).

The leuco dye capable of imparting a blue dye of the present invention (hereinafter referred to as "leuco dye of the present invention") may be any compound which gives a blue dye after development, and one which gives a blue dye after black and white development. Preferred are compounds represented by the following general formula (1).

[0045]

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In the formula, W is -NR ₁ R ₂ , -OH or -OZ
Wherein R ₁ and R ₂ each represent an alkyl group or an aryl group, and Z represents an alkali metal ion or a quaternary ammonium ion. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. Z ₁ and Z ₂ each represent a nitrogen atom or C (R ₃ );
It represents ₁ and Z ₂ and atomic group required to construct aromatic carbocyclic 5-6 membered together with the carbon atoms, or an aromatic heterocyclic ring adjacent thereto. R ₄ is a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a carboxyl group,
Represents a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R represents an aliphatic group or an aromatic group, p represents an integer of 0 to 2, and CP ₁ represents the following group.

[0047]

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In the formula, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on a benzene ring. R _{5 to} R ₈ may be bonded together to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R
₁₁ represents an alkyl group, an aryl group or a heterocyclic group, respectively. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ are each R
₁₀ and R ₁₁ as synonymous. R ₁₅ has the same meaning as R ₁₂ . R
₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. Y ₁ represents an atom group necessary for constructing a 5- to 7-membered monocyclic or condensed-ring nitrogen-containing heterocycle together with two nitrogen atoms. R ₁₉ and R ₂₀
Represents an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ are each the same meaning as R ₁₉ and R _20. R ₂₄ has the same meaning as R ₄ . R ₂₅ , R ₂₇ and R ₂₈ each represent a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ .

R ₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ respectively. R ₃₀ has the same meaning as R ₄ . R ₃₄ , R
₃₅ and R ₃₆ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ respectively. R
₃₃ has the same meaning as R ₄ . R ₃₈ , R ₃₉ and R ₄₀ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ respectively. R ₃₇ has the same meaning as R ₄ . R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ respectively. R ₄₄ has the same meaning as R ₂₆ . * Represents a bonding point between CP ₁ and other partial structures in the general formula (1).

In the general formula (1), W is preferably -NR ₁ R ₂ . Examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, and a butyl group. These may be further substituted,
Preferred substituents include a hydroxyl group and a sulfonamide group. The aryl group represented by R ₁ and R ₂ includes a phenyl group. Examples of the monovalent substituent represented by R ₃ include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, etc.), a cycloalkyl group (Eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2
-Phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.) An aryloxy group (eg, phenoxy group etc.), a cyano group, an acylamino group (eg, acetylamino group, propionylamino group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), an arylthio group (eg, , Phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group) Etc.), sulfamoylamino group (dimethylsulfamoylamino group ), A carbamoyl group (eg, a methylcarbamoyl group, an ethylcarbamoyl group, a dimethylcarbamoyl group, etc.), a sulfamoyl group (eg, an ethylsulfamoyl group, a dimethylsulfamoyl group, etc.), an alkoxycarbonyl group (eg, a methoxycarbonyl group, Ethoxycarbonyl group and the like), aryloxycarbonyl group (for example, phenoxycarbonyl group),
Sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.) ), A hydroxyl group, a nitro group, an imide group (eg, a phthalimido group), a heterocyclic group (eg, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, etc.). Z
Examples of the alkali metal represented by are sodium and potassium. Examples of the quaternary ammonium include ammonium having 8 or more carbon atoms, such as trimethylbenzylammonium, tetrabutylammonium, and tetradecylammonium. Examples of the 5- to 6-membered aromatic carbon ring formed with X, Z ₁ and Z ₂ and carbon atoms adjacent thereto include a benzene ring and a naphthalene ring, and a benzene ring is preferable. Further, as the aromatic hetero ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a tetrazine ring, a pyrrole ring,
Examples thereof include a furan ring, a thiophene ring, a thiazole ring, an oxazole ring, an imidazole ring, a thiadiazole ring, and an oxadiazole ring, and a pyridine ring is preferable.

Examples of the substituent capable of substituting on the benzene ring represented by R _{5 to} R ₈ include groups having the same meaning as the above-mentioned monovalent substituent represented by R ₃ . Preferred are an alkyl group and an acylamino group. Examples of the 5- to 7-membered ring formed by combining R ₅ and R ₆ and R ₇ and R ₈ include an aromatic carbon ring and a heterocyclic ring, and preferably a benzene ring. Examples of the alkyl group represented by R ₁₀ and R ₁₁ include a methyl, ethyl, propyl, and butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. 5- or 6-membered aromatic heterocyclic ring having at least one kind of sulfur, nitrogen and nitrogen atoms in the ring (for example, a 6-membered azine such as a pyridine, pyrimidine, pyrazine ring and the like, and its benzolog: pyrrole, thiophene, furan and its benzerog) : 5-membered ring azoles such as imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, thiadiazole, oxadiazole and the like, and benzolog). Preferred examples of R ₁₀ and R ₁₁ include a phenyl group, a pyrazolyl group, and a pyridyl group. R
Examples of the alkyl group represented by ₁₆ include a methyl group, an isopropyl group, a pentyl group, a t-butyl group and the like, examples of the aryl group include a phenyl group and a naphthyl group, and examples of the sulfonyl group include methine sulfonyl Group, benzenesulfonyl group, etc., as the aryloxycarbonyl group, a phenoxycarbonyl group, etc., as the alkoxycarbonyl group, an ethoxycarbonyl group, etc., and as the carbamoyl group, a diethylaminocarbamoyl group, etc. Can be Examples of the nitrogen-containing hetero ring represented by Y ₁ include each of imidazole, triazole, and tetrazole rings and benzo-fused rings thereof. Examples of the alkyl group represented by R ₁₉ and R ₂₀ include a methyl group, a pentyl group and a t-butyl group, and examples of the aryl group include a phenyl group and a naphthyl group. Examples of the substituent represented by R ₂₅ , R ₂₇ and R ₂₈ include a phenyl group, a methyl group, a benzoyl group, a phenoxy group and an ethoxy group. As the aliphatic group represented by R, a hexyl group, a dodecyl group and the like are preferably exemplified, and as the aromatic group, a P-toluyl group, a dodecylphenyl group and the like are preferably exemplified. p is preferably 0 or 1.

The compounds represented by the general formula (1) will be specifically described below, but it should not be construed that the invention is limited thereto.

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The amount of the leuco dye added in the present invention is such that the density becomes 1/10 or less, preferably 1/20 or less of the silver image density. The concentration measurement here is Macbet
h-concentration type TR-927 (Visual Densit)
y). The lower limit of the dye image density is 0.01, particularly 0.02.

[0068] If the leuco dye contained in the photosensitive ^{material, 5mg / m 2 ~300mg / m} 2 is preferred. Preferably from ^{10mg / m 2 ~100mg / m 2} .

The leuco dye of the present invention may be added to any of the hydrophilic colloid layers including the silver halide emulsion layer constituting the present invention, but preferably the silver halide emulsion layer or an adjacent layer thereof is added. good.

When the leuco dye of the present invention is water-soluble, it can be added to the hydrophilic colloid as an aqueous solution having an appropriate concentration. When the compound of the present invention is soluble in an organic solvent, a low-boiling organic solvent or an organic solvent miscible with water, such as alcohols, ethers, glycols, ketones, esters and amides, adversely affects photographic properties. Can be added to the hydrophilic colloid constituting the photographic layer as a solvent.

As another method for introducing the leuco dye of the present invention into the hydrophilic colloid constituting the photographic layer, a method known as a method for emulsifying a color coupler and adding the emulsified color coupler into the hydrophilic colloid layer may be used. it can. That is, US Pat. No. 2,322,027 or US Pat. No. 2,304,9
The compound can be dissolved in an organic solvent, emulsified and dispersed using a surfactant, and the emulsified dispersion can be added to a hydrophilic colloid for photography according to a method described in JP-A No. 39 or the like. The organic solvent for this purpose has a boiling point of 175 ° C.
High boiling organic solvent or boiling point 30 ° C to 150 ° C
Are used alone or in a mixture of both at an arbitrary ratio. As the low boiling organic solvent, those described above can be used. Further, as the high boiling organic solvent, di-n-butyl phthalate, benzyl phthalate, triphenyl phosphate,
Tri-o-cresyl phosphate, diphenyl mono-p
-Tert-butylphenyl phosphate, monophenyl-di-p-tert-butylphenylphosphate,
2,4-di-t-amylphenol, N, N-diethyllauramide, trihexyl phosphate and the like can be used.

The leuco dye may be added in the form of fine solid particles.

The step of introducing the leuco dye of the present invention into a hydrophilic colloid constituting a photographic light-sensitive material may be any of the steps for producing a photographic light-sensitive material. A step of preparing a coating solution for use is desirable.

The oils in the present invention are those having a boiling point of 12
Oils having a solubility in water of 0 ° C. or higher (preferably 160 ° C. or higher) at 25 ° C. of 10 weight or less and being liquid at 25 ° C. are exemplified.

In the present invention, the amount of the oils to be used is from 0.2 to 0.2 by weight based on the amount of gelatin in the hydrophilic colloid layer.
1.0, and more preferably 0.3 to 0.8.

These oils are dispersed in the form of oil droplets in a hydrophilic colloid layer containing gelatin. Regarding the average particle size of the dispersed oil droplets, whether the individual particle size distribution is wide or narrow, It is good, but when the particle size of 0.1 to 0.4 μm occupies 75% or more of the whole, the object effect of the present invention is favorably exhibited. Various surfactants can be used for dispersion. For example, US Pat.
No. 32,027, No. 2,801,170, No. 2,80
Anionic surfactants described in No. 1,171, JP-B-48
No.-9979 discloses anionic and nonionic surfactants and the like.

Hereinafter, typical examples of the oils used in the present invention will be described.

Diethyl adipate, dibutyl adipate, diisobutyl adipate, di-n-hexylethyl adipate, dioctyl adipate, dicyclohexyl azelate, di-2-ethylhexyl azelate, dioctyl sebacate, diisooctyl sebacate, dibutyl lexinate, Octyl stearate, dibenzyl phthalate, tri-o-cresyl phosphate, diphenyl-mono-p-tert-butylphenyl phosphate,
Monophenyl-di-o-chlorophenyl phosphate,
Monobutyl-dioctyl phosphate, 2,4-di-n
-Amylphenol, 2,4-di-tert-amylphenol, 4-n-nonylphenol, 2-methyl-4
-N-octylphenol, N, N-diethylcaprylamido, N, N-diethyllauramide, glycerol trilopionate, glycerol tributyrate,
Glycerol monolactate acetate, tributyl citrate, acetyl triethyl citrate, di-2-ethylhexyl adipate, dioctyl sebacate, diisooctyl azelate, diethylene glycol dibenzoate, dipropylene glycol benzoate, triethyl citrate, tri (2-ethylhexyl) Citrate, acetyl tri-n-butyl citrate, di (isotesyl) 4,5-epoxytetrahydrophthalate, oligovinyl ethyl ether, dibutyl phthalate, polyethylene oxide (n> 16), glycerol tributyrate, ethylene glycol diprolobionate, Di (2-ethylhexyl) isobutyrate, butyl laurate, tri- (2-ethylhexyl) phosphate, triphenyl phosphate Tricresyl phosphate,
Silicon oil, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, isooctyl phthalate, diamino phthalate, di-n-octyl phthalate, diamyl naphthalene, triamyl naphthalene, monocaprin, monolaurin, monomyristine, monopalmitin, mono Stearin, monoolein,
Dicaprin, diproline, dimyristin, dipalmitin, distearin, diolein, 1-stearo-2-palmitin, 1-palmito-3-stearin, 1-palmito-2-stearin, triacetin, tricaprin, trilaurin, trimyristin, tripalmitin, tri Stearin, triolein, tripetroserin, trielsin, triricinolein, linoleodistearin, oleozielsin, linoleozieresin, palmitooleinorenin, paraffin, linseed oil, soybean oil, eno oil, kiri oil, asami oil, kaya oil , Walnut oil, soy sauce oil, poppy oil,
Dry oils such as sunflower oil, azusa oil, kwai oil and safflower oil; semi-dry oils such as cottonseed oil, corn oil, sesame oil, rapeseed oil, rice bran oil, lotus oil, mustard oil, pumpkin oil, dehydrated castor oil, etc. Peanut oil, olive oil, camellia oil, sasanqua oil, tea oil, castor oil, hydrogenated castor oil, almont oil, bundling oil, ben oil, large apricot oil and the like.

Further, compounds represented by the following general formula can also be used as oils in the present invention.

[0080]

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In the formula, R represents an alkyl group having 1 to 8 carbon atoms.

Others JP-A-50-23823, 50
-62632, 51-26035, 51-26
Compounds other than those described in JP-A Nos. 036 and 51-26037 can be used in the same manner.

Among them, esters such as adipic acid, phthalic acid, sebacic acid, succinic acid, fumaric acid, mazeleiic acid, isophthalic acid and phosphoric acid, glycerin esters and paraffins do not adversely affect photographic light-sensitive materials.
It can be conveniently used because it is easily available, chemically stable and easy to handle. Further, tricresyl phosphate, dibutyl phthalate, di-n-octyl phthalate, tri-o-cresyl phosphate, glycerol tripropionate, dioctyl sebacate, paraffin, and silicone oil are particularly preferred oils in the present invention.

In forming oil droplets in the present invention, a water-soluble or water-insoluble organic low-boiling compound may be used in combination, if necessary. After the photographic light-sensitive material is coated and dried, it evaporates and almost no longer exists in the layer. Specific examples of these include, for example, methanol, ethanol, propyl alcohol, fluorinated alcohol, acetonitrile, dimethylamide, dioxane, methyl isobutyl ketone, diethylene glycol monoacetate, chloroform, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexynol And cyclohexanetetrahydrofuran.

In the present invention, the oil droplets are mainly composed of the above-mentioned oils. The lipophilic photographic coupler, ultraviolet absorber, development inhibitor releasing compound, hydroquinone derivative,
An image fading inhibitor or the like may be contained in the oil droplets. However, when a large amount of lipophilic photographic additive is used, the pressure resistance of the silver halide photographic light-sensitive material is deteriorated.

The oils used in the present invention are those which can be dispersed in a coating solution without being mixed with the solution and which do not lose oil droplets even when the coating solution is coated and dried under ordinary conditions. Is selected. Among them, preferred are those having a melting point of 50 ° C. or lower alone or in combination of two or more, and when used alone or in combination of two or more, 25
Those that are liquid at ° C. are more preferred.

In the present invention, oil droplets due to oils are as follows.
Oil droplets may be created simultaneously using seeds or two or more,
You may mix and use what was separately emulsified and dispersed.

Hereinafter, specific examples of the oil compound dispersion will be described.

Dispersion average particle size O-1: Tris (isopropylphenyl) phosphate 0.20 μ O-2: Trixyleryl phosphate 0.25 μ O-3: Tributyl phosphate 0.15 μ O-4: Dioctyl phthalate 0.15 μ O -5: dibutyl phthalate 0.20 µ O-6: dihexyl phthalate 0.15 µ O-7: tricresyl phosphate 0.20 µ O-8: o-acetyltriethyl citrate 0.15 µ O-9: N, N-dimethyl Laurylamide 0.10 μ The present invention is also directed to a silver halide photographic material having a photosensitive silver halide emulsion layer on both sides of a support. The silver halide photographic light-sensitive material comprises, for example, a photosensitive emulsion layer on a support coated with an undercoat layer as a photographic component layer, and a hydrophilic colloid layer on which at least one intermediate layer, a protective layer, an antistatic layer and the like are provided. Layers or more may be coated constituent layers. As a preferred embodiment of the present invention, a photosensitive emulsion layer is provided on a support, and a protective layer is provided on the uppermost layer as a hydrophilic colloid layer on the photosensitive emulsion layer. The oil of the present invention is dispersed in the protective layer. It is a form.

The silver halide photographic light-sensitive material of the present invention includes:
It is advantageous to use gelatin and gelatin derivatives as silver halide binders. As gelatin, acid-treated gelatin may be used in addition to lime-processed gelatin, and hydrolysates and oxygen-decomposed products of gelatin can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid alkane salts, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are reacted with gelatin. What is obtained is used.

The photosensitive silver halide emulsion of the silver halide photographic material of the present invention may be silver bromide, silver iodobromide, or a silver iodochlorobromide emulsion containing a small amount of silver chloride.

The emulsion used in the silver halide photographic light-sensitive material of the present invention preferably contains tabular silver halide grains described later. The silver halide grains themselves are known and can be produced by a known method. Can be.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. Monodisperse here means, when the average particle diameter is measured by an ordinary method,
Silver halide grains in which at least 95% of the grains by number or weight are within ± 40%, preferably within ± 30% of the average grain size.

The particle size distribution of the silver halide grains may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition between the inside and the outside. For example, a high silver iodide core portion is coated with a low silver iodide shell layer to form a clear two-layer structure. The core / shell type monodisperse emulsion may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is obtained by, for example, using a seed crystal as a method for obtaining a monodisperse emulsion and supplying silver ions and halide ions using the seed crystal as a growth nucleus. Emulsions may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has a total projection area of 70% of the silver halide emulsion layer.
% Or more, more preferably 90% or more, are tabular grains having an aspect ratio (ratio of grain diameter / grain thickness) of 3 or more and 20 or less, and preferably silver halide grains having an aspect ratio of 4 or more and 10 or less. .

The advantages of the tabular silver halide grains are that they can improve the spectral sensitization efficiency and improve the graininess and sharpness of an image.
No. 2,157, U.S. Pat.
No. 434,226, etc., and emulsions can be prepared by referring to the methods described in these publications.

The emulsions described above are either of a latent image type in which a latent image is formed on the grain surface, an internal latent image type in which a latent image is formed inside the grain, or an emulsion in which a latent image is formed on both the surface and the inside. It may be. These emulsions can be prepared at the stage of physical ripening or grain preparation by using, for example, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt and the like. Good.

The emulsion may be subjected to a water washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. As a preferred water washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group, or a method using an aggregating polymer agent or the like is mentioned as a particularly preferable desalting method.

Various photographic additives can be used in the silver halide photographic light-sensitive material according to the present invention. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978), N
o. No. 18716 (November 1979) and the same No. 30
8119 (December 1989). The compound types and locations described in these three RDs are described below.

[0101]

[Table 1]

As a support that can be used in the light-sensitive material of the present invention, for example, a polyethylene terephthalate film is used. The surface of the support is provided with an undercoat layer or a corona discharge to improve the adhesion of the coating layer. , Ultraviolet irradiation or the like.

Hereinafter, the processing method of the light-sensitive material of the present invention will be described.

In the developing solution in the processing method of the present invention, an organic reducing agent can be used in addition to sulfite as a preservative. In addition, bisulfite adducts of chelating agents and hardeners can be used. It is also preferable to add compounds described in Japanese Patent Application Nos. 4-92947 and 5-96118 (general formulas [4-a] and [4-b]) as silver sludge inhibitors. The addition of a cyclodextrin compound is also preferable, and the compounds described in JP-A-1-124852 are particularly preferable.

An amine compound can be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferred. Further, it is necessary to use a buffer, and as the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate Sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

Examples of development accelerators include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, ionic compounds, and the like. Mesoionic compounds, imidazoles and the like can be added as needed.

As an antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
-Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-
Examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindene, and adenine, and a typical organic antifoggant includes 1-phenyl-5-mercaptotetrazole.

Further, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, and other JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of a developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkali metal such as KBr, an organic inhibitor, and a development accelerator are used.

The processing temperature of the developer is preferably 25 to 5
At 0 ° C, more preferably 30 to 40 ° C. The total processing time in the present invention is 30 seconds or less in Dry to Dry, and preferably 25 seconds or less. The term "total processing time" as used herein refers to the total processing time including the steps of developing, fixing, washing and drying the photosensitive material.

[0111]

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

Example 1 (Preparation of Hexagonal Tabular Seed Emulsion) Pure silver bromide hexagonal tabular seed emulsion EM-A was prepared by the following method.

[0113] A1 ossein gelatin 60.2g Distilled water _{20.0l HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5-7) 10% aqueous methanol solution 5.6 ml KBr 26.8 g 10% H ₂ SO ₄ 144 ml B1 silver nitrate 1487.5 g Make up to 3500 ml with distilled water C1 KBr 1050 g Make up to 3500 ml with distilled water D1 1.75 N aqueous KBr solution Silver below Potential control amount At 35 ° C, JP-B-58-58288, 58-58288
Using a mixing stirrer described in Japanese Patent No. 58289, 64.1 ml of each of the solution B1 and the solution C1 was added to the solution A1 by a simultaneous mixing method over a period of 2 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. over a period of 60 minutes, and the solution B1 and the solution C1 were again mixed by the simultaneous mixing method.
Each was added at a flow rate of 68.5 ml / min for 50 minutes.
During this time, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was measured at +6 mV using the solution D1.
It controlled so that it might become. After completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately after desalting and washing, the seed emulsion EM was added.
-A. The seed emulsion EM-A thus prepared is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 for 90% or more of the total projected area of silver halide grains, and the average thickness of the hexagonal tabular grains. Electron microscopy revealed that the average diameter (in terms of circular diameter) was 0.07 μm, the average diameter was 0.5 μm, and the coefficient of variation was 25%.

(Preparation of silver bromoiodide emulsion EM-1)
Tabular pure silver bromide emulsions were prepared using the various solutions.

[0116] A2 ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) 10 % Methanol aqueous solution 1.25 ml seed emulsion EM-A 2.65 mol equivalent Make up to 3000 ml with distilled water B2 3.50 N AgNO ₃ aqueous solution 1760 ml C2 KBr 737 g Make up to 1760 ml with distilled water D2 1.75 N KBr aqueous solution Below silver potential control amount At 60 ° C, JP-B-58-58288, 58-58288
Using the mixing stirrer described in the specification of Japanese Patent No. 58289, the total flow rate of the solution B2 and the solution C2 to the solution A2 is doubled by the simultaneous mixing method (double jet method) so that the flow rate at the end of the addition becomes three times the flow rate at the start of the addition. In this way, 110 minutes were required to perform the additive growth.

During this time, the silver potential was increased by +40 using solution D2.
It controlled so that it might be set to mV.

After completion of the addition, in order to remove excess salts,
Precipitation and desalting were performed by the following method.

[0119] 1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
20 g / AgX of 1 mol of agglomerated gelatin agent G-3 (gelatin with amino group benzoylated (exemplified agglomerated gelatin agent G-3 described in JP-A-2-280139, page 3)) was added, and 56 wt% acetic acid was added. The pH is dropped to 4.30, the mixture is left to stand, and decantation is carried out.
Stir and decant after stirring for 3 minutes. 3. Repeat the above step 2 once more. Thereafter, 15 g of gelatin / 1 mol of AgX, sodium carbonate and water were added, and the mixture was adjusted to pH 6.0 and dispersed.
/ AgX 1 mol.

When about 3,000 silver halide grains of the obtained emulsion EM-1 were observed and measured by an electron microscope to analyze the shape, a hexagonal flat plate having an average equivalent circle diameter of 0.59 μm and an average thickness of 0.17 μm was obtained. Particles with a coefficient of variation of 2
4%.

(Preparation of silver iodide fine particles) A4 ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water B4 AgNO ₃ 360 g Make up to 605 ml with distilled water C4 KI 352 g Make up 605 ml with distilled water Solution A4 in a reaction vessel The solution B4 and the solution C4 were added at a constant speed over 30 minutes by the simultaneous mixing method while stirring at 40 ° C.

The pAg during the addition was kept at 13.5 by a conventional pAg control means. The formed silver iodide has an average grain size of 0.06.
It was a mixture of μm β-AgI and γ-AgI.

This emulsion is called a silver iodide fine grain emulsion.

(Preparation of solid fine particle dispersion of spectral sensitizing dye) The following spectral sensitizing dyes (A) and (B) were added at a ratio of 100: 1 to water previously adjusted to 27 ° C., and a high-speed stirrer ( (Dissolver) at 3,500 rpm for 30 to 120 minutes to obtain a solid fine particle dispersion of the spectral sensitizing dye. At this time, the sensitizing dye (A) was adjusted to have a concentration of 2 wt%.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine salt anhydride sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3, 3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydrous <Sensitization> Emulsion EM-1 was subjected to spectral sensitization and chemical sensitization in the following manner.

After the emulsion was heated to 60 ° C., the above solid fine particle dispersion was added so that the sensitizing dye (A) was 460 mg per mol of silver, and ammonium thiocyanate was added to the emulsion at 7.0 per mol of silver. × 10 ^-4 mol, and 1.45 mg of potassium chloroaurate, 1.50 mg of sodium thiosulfate and 3.0 × 10 ^-6 mol of triphenylphosphine selenide per mol of silver were added per mol of silver. After optimal chemical ripening, the above silver iodide fine grain emulsion was added in an amount of 3 × 10 ^-3 mol / Ag 1 mol, and
6-methyl-1,3,3a, 7-tetrazaindene (T
AI) stabilized at 3 × 10 ^-2 mol. Emulsion E
M-1 '.

<Preparation of undercoated support><Preparation of support> After adding a transesterification catalyst to 100 parts of dimethyl naphthalene-2,6-dicarboxylate and 60 parts of ethylene glycol, sodium dodecylbenzenesulfonate 1 .2 parts, 0.8 parts of polyethylene glycol having a molecular weight of 8000, and 0.01 parts of thyroid were added,
The polyethylene-2,6-naphthalate obtained by performing the polycondensation is melt-extruded to obtain an unstretched film of 170.
After stretching 4.2 times at 4.degree.
It was stretched twice.

The heat setting was at 255 ° C. for 10 seconds. Thus, a support having a thickness of 175 μm (A-1) was obtained.
Also, by changing the degree of stretching, the thickness of 100, 120
A support of μm (A-2, 3) was also prepared.

Further, supports A-4 to A-7 shown in Table 2 were also prepared.

<Underlining treatment> JP-A-52-104913
No. 1 of the sample No. Subbing was performed according to the method of No. 9.

When the support is formed, a thickness of 175
With respect to those having a thickness of μm, dimethyl naphthalene-2,6-dicarboxylate and dimethyl terephthalate were added in a ratio of 100: 0 (the above-mentioned support A-1), 80:20, 60:40, 4
Supports (A-4, 5, 6, 7) polymerized in the same manner as in 0:60 and 20:80 were also prepared.

The undercoating process was performed in the same manner as described above.

As a comparative support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%,
175 μm, 120 μm (A-8) of a copolymer aqueous dispersion obtained by diluting a copolymer composed of three kinds of monomers of 40 wt% of butyl methacrylate to be 10 wt% and applying as a subbing liquid , 9) to produce a polyethylene terephthalate film.

<Preparation of photosensitive material sample> The following crossover cut layers were formed on both sides of each support prepared as described above.
Samples were prepared as shown in Table 2 by simultaneously coating the emulsion layer, the intermediate layer, and the protective layer on both surfaces uniformly at a speed of 150 m / min and then drying so that the following coating amounts were obtained.

First Layer (Crossover Cut Layer) Solid Fine Particle Dispersion Dye (AH) 30 mg / m ² Gelatin 0.2 g / m ² Dextrin (average molecular weight 1000) 0.05 g / m ² Dextran (average molecular weight 40,000) 0 0.05 g / m ² sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size) 10 mg / m2 ^Second layer (emulsion layer) The following various additives were added to the emulsion EM-1 'obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone ( Molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Leuco dye Amount shown in Table 2 Nitrophenyl -Triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² dextran (average molecular weight 40000) 0.1 g / m ² Hardener (B) 1.0 g / m ² However, gelatin added was 1.0 g / m ^2. It was adjusted to m ^2.

Third layer (intermediate layer) Gelatin 0.4 g / m ² formaldehyde 10 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² bis-vinylsulfonylmethyl Ether 18 mg / m ² Latex (L) 0.05 g / m ² Sodium polyacrylate 10 mg / m ² Compound (S-1) 3 mg / m ² Compound (K) 5 mg / m ² Fourth layer (protective layer) Gelatin 0 Matting agent comprising 0.6 g / m ² polymethyl methacrylate (area average particle size 7.0 μm) 50 mg / m ² formaldehyde 10 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² bis-vinylsulfonyl methyl ether 18 mg / m ² latex (L) 0.1 g / m ² polyacrylamide (flat Equivalent molecular weight 10000) 0.05 g / m ² Sodium polyacrylate 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² polysiloxane (S1) 10 mg / m ² C ₉ F ₁₉ —O— (CH ₂ CH ₂ O) ₁₁ H 3 mg / m ² C _{8 F 17 SO 2 N <(} C 3 H 7) (CH 2 CH 2 O) 15 H 2mg / m 2 C 8 F 17 SO 2 N <(C 3 H 7) (CH 2 CH 2 O) 4 (CH ₂ ) ₄ SO ₃ Na 1 mg / m ² Hardener (B) 1.5 mg / m ²

[0138]

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[0139]

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[0140]

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The amount of the raw material was one side, and the amount of silver applied was adjusted to 1.5 g / m ² as one side.

<< Evaluation Method >><Granularity> SR-DFN was performed using an automatic developing machine modified from the SRX-503 automatic developing machine so as to have the following processing time.
The sample was subjected to X-ray exposure at a developing temperature of 35 ° C. at a developing temperature of 35 ° C. so that a large-angle size (35.6 × 35.6 cm) of the sample was uniformly exposed to a concentration of 1.2. After the developed sample was kept at 50 ° C. and 80% RH for 7 days, it was observed with Schaukasten, and the graininess was visually evaluated. The replenishment rate of the processing solution is 125 for both the developer and the fixer.
It was treated at ml / m ² .

Developing time: 8 seconds Fixing time: 6.2 seconds Washing time: 4 seconds Between washing and drying (squeeze): 3.2 seconds Drying time: 8.6 seconds Total processing time: 30 seconds The evaluation criteria are as follows. It is on the street.

1: There is a considerable feeling of roughness which affects the diagnosis. 2: There is a feeling of roughness. 3: There is a feeling of slight roughness. 4: Very fine and good granularity. The results are shown in Table 2.

[0145]

[Table 2]

As is clear from Table 2, the samples of the present invention have excellent graininess.

Example 2 A sample was prepared in the same manner as in Example except that the oil shown in Table 3 was added to the intermediate layer. The silver tone and the devitrification were evaluated as described below.

<Silver tone> The large size (3
(5.6 × 35.6 cm) was uniformly exposed to X-rays so that the density became 1.2, and then SR was processed using an automatic developing machine which was modified from an SRX-503 automatic developing machine to have the following processing time. Processing was carried out with a DFN processing solution at a development temperature of 35 ° C.
The processing solution was replenished at a rate of 125 ml / m ² for both the developing solution and the fixing solution.

Developing time: 8 seconds Fixing time: 6.2 seconds Washing time: 4 seconds Between washing and drying (squeeze): 3.2 seconds Drying time: 8.6 seconds Total processing time: 30 seconds The surface temperature of the heat roller is 60
Drying was performed at ° C. As the heat roller, a roller using a halogen heater as a heat source coated with aluminum Teflon was used.

The developed sample thus obtained was
After storing at 50 ° C. and 80% RH for 7 days, observation was carried out using a Schaukasten, and the silver tone due to transmitted light was visually evaluated.

4: Pure black 3: Slightly reddish black 2: Reddish black 1: Yellowish black <Devitrification> Unexposed by the same processing method as in the above silver tone evaluation. Each sample was processed. The transparency of the obtained sample was visually evaluated.

4: No deterioration in transparency 3: Very slightly milky 2: Slightly milky 1: Milky white The results are shown in Table 3.

[0153]

[Table 3]

As is clear from Table 3, the sample of the present invention has excellent silver tone and devitrification.

[0155]

According to the present invention, a silver halide photographic light-sensitive material excellent in graininess, silver color and devitrification and capable of ultra-rapid processing can be provided.

Claims (2)

[Claims] Claims: 1. On at least one side of a transparent support,
In a silver halide photographic light-sensitive material having a hydrophilic colloid layer including at least one light-sensitive silver halide emulsion layer, the hydrophilic colloid layer reacts with an oxidized form of a developing agent to form a leuco dye which gives a blue dye. A silver halide photographic material, wherein the transparent support is a biaxially stretched polyester film substantially containing polyethylene-2,6-naphthalate. 2. On at least one side of the transparent support,
In a silver halide photographic material having a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer, a non-photosensitive hydrophilic material containing an oil between the photosensitive silver halide emulsion layer and the uppermost layer A silver halide photographic material having a colloid layer and wherein the transparent support is a biaxially stretched polyester film substantially containing polyethylene-2,6-naphthalate.