JP3508080B2 - Silver halide photographic material and processing method thereof - Google Patents

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 a method for processing the same, and is particularly high even when subjected to ultra-rapid processing in a total processing time of 25 seconds or less in an environment in which the replenishment amount of a developing solution is reduced. The present invention provides a silver halide photographic light-sensitive material which has excellent sensitivity and pressure resistance, and is less susceptible to film cracking and fog deterioration at low humidity, and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, due to the progress of electronics, the shortening of access time to images has been dramatically advanced, and rapid processing is required for silver halide photographic light-sensitive materials.

In order to impart rapid processability, the amount of gelatin used as a binder, which has been conventionally used to disperse and protect silver halide grains, is reduced, and the developing rate, fixing rate, washing rate and drying rate in photographic processing are reduced. Techniques for raising are known. However, when the amount of gelatin used is reduced, the highly sensitive silver halide grains become even weaker against external pressure, and when processed with an automatic processor, it is called a roller mark, which is called the roller mark of the transport roller in the developing tank of the automatic processor. There is a problem that a large number of fine spot-like density unevenness is generated due to the pressure caused by the unevenness, and the problem becomes remarkable especially when performing an ultra-rapid processing such that the total processing time is 25 seconds or less.

Further, in recent years, global environmental pollution has been taken up as a global problem, and interest in wastes has been increasing in Japan and overseas, and the responsibility of a company is being questioned. Under such circumstances, reduction of photographic processing waste liquid has become an urgent issue.

In general, each constituent layer of a photographic light-sensitive material, such as an undercoat layer or a hydrophilic colloid layer, does not have a bad influence on the photographic light-sensitive properties, but also the physical properties of the film, such as the adhesive strength before and after development, the development. Predetermined strength is also required in terms of dimensional stability before and after, dimensional stability against humidity and heat, flexibility, pressure resistance, and drying property. Therefore, conventionally, when a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer or a protective layer is coated on a support, a polymer latex or colloidal silica obtained by polymerizing various monomers in the hydrophilic colloid layer. Various attempts have been made to improve the physical properties of a hydrophilic colloid film formed by containing the above-mentioned dimensional stability, scratch strength, flexibility, pressure resistance and drying property.

From this point of view, US Pat. No. 2,37,37
In US Pat. No. 6,005, vinyl acetate polymer latex is used, in US Pat. No. 3,325,286, alkyl acrylate polymer latex is used, and in Japanese Patent Publication No. 45-5331, n-butyl acrylate, ethyl acrylate, styrene. The use of polymer latices such as butadiene, butadiene, vinyl acetate and acrylonitrile, the use of polymer latices of alkyl acrylate, acrylic acid and sulfoalkyl acrylate in JP-B-46-22506, and JP-A-51-130217 The use of a polymer latex of acrylamido-2-methylpropanesulfonic acid is disclosed in Japanese Examined Patent Publication No. 47-50723.
The use of colloidal silica in JP-A-61-140939 is disclosed in JP-A-61-236544 and JP-A-1-1.
No. 177033 proposes to use a composite latex containing acrylic acid ester and colloidal silica as components. However, these polymer latices and colloidal silica have poor compatibility with hydrophilic colloids and cannot be added in a large amount, the adhesive strength between layers is reduced, and the scratch resistance is deteriorated. There is a problem that the quality of the photographic light-sensitive material is remarkably deteriorated because the material is cracked or the photographic performance is deteriorated.

Further, even when the composite latex described in JP-A No. 1-177033 is used, the occurrence of cracks is moderated but is not sufficient, and the compatibility with the hydrophilic colloid is not improved and a large amount is obtained. However, there is a problem that the scratch resistance at the time of development is deteriorated and the photographic performance is deteriorated.

[0008]

In contrast to the problems described above, an object of the present invention is to have a high sensitivity and an excellent pressure resistance even in a treatment with a low replenishing amount in consideration of the environment, and to have a low humidity. SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which is free from film cracking and has suitability for ultra-rapid processing with less deterioration of fog, and a processing method thereof.

[0009]

The above object of the present invention can be achieved by the following constitutions.

(1) In a silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer, at least one metal oxide is contained in at least one of the silver halide emulsion layers . A dextrin or cyclodene having a number average molecular weight of 20,000 or less is contained in the silver halide emulsion layer and / or at least one non-photosensitive hydrophilic colloid layer containing a composite polymer composed of grains and a hydrophobic polymer.
A silver halide photographic light-sensitive material containing a water-soluble polymer selected from xistrin and its derivatives , wherein the hydrophobic polymer is at least an ester having 6 or more carbon atoms.
Halogen, characterized in that it consists of monomer selected from methacrylic acid esters with acrylic acid esters or glycidyl group with a monomer and a glycidyl group selected from acrylic acid esters or methacrylic acid esters having a group Silver halide photographic light-sensitive material.

(2) The silver halide photographic light-sensitive material as described in the above item (1), wherein the water-soluble polymer is dextrin.

(3) Item (1) or (2) above, wherein the amount of gelatin in the total hydrophilic colloid layer on one side of the support is 1.0 to 2.0 g / m ^2. Silver halide photographic light-sensitive material.

(4) The silver halide photographic light-sensitive material described in any one of the above items (1) to (3) is used in an amount of 35 to 98 ml of development replenisher per 1 m ^{2 of the} silver halide photographic light-sensitive material. A method of processing a silver halide photographic light-sensitive material, which comprises processing with an automatic processor having a total processing time of 10 to 25 seconds.

The present invention will be described in more detail. Examples of the inorganic particles used in the composite polymer of the present invention include metal oxides, nitrides, sulfides and the like, but metal oxides are preferable. As the metal oxide, Na, K, Ca, B
a, Al, Zn, Fe, Cu, Ti, Sn, In, W,
Y, Sb, Mn, Ga, V, Nb, Tu, Ag, Bi,
Single or complex oxide particles of metals such as B, Si, Mo, Ce, Cd, Mg, Be and Pb are preferable, and Y, Sn, Ti, Al, V, Sb, In and Mn are particularly preferable.
Single or complex oxide particles of Ce, B and Si are particularly preferable from the viewpoint of compatibility with the emulsion.

Such metal oxide particles can be preferably used in either crystalline or amorphous form, but amorphous metal oxide particles are particularly preferable.

The average particle size of the metal oxide particles used in the present invention is preferably 0.5 nm to 3000 nm, particularly preferably 3 nm to 1000 nm. Such metal oxide particles are preferably dispersed in water and / or a water-soluble solvent, and particularly preferably water and alcohols such as methanol, ethanol and isopropanol.

The addition amount of the metal oxide of the present invention is preferably 1 to 2000% by weight, particularly preferably 30 to 1000% by weight, based on the hydrophobic polymer.

Examples of preferable metal oxides are shown below.

[0019]

[Table 1]

Examples of the hydrophobic monomer forming the hydrophobic polymer compound forming the composite polymer of the present invention include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes and crotons. Acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, various unsaturated acids Examples of the hydrophobic monomer include one kind or a combination of two or more kinds. The hydrophobic monomer forming the hydrophobic polymer compound of the present invention is preferably acrylic acid ester and / or methacrylic acid ester, and styrene, and the ester group has 6 or more carbon atoms. Particularly preferred. It is preferable to use a hydrophobic monomer having a glycidyl group as the hydrophobic monomer, at least 1.0 to 20% by weight, particularly preferably 20 to 20% by weight.
It is 100 wt%.

The hydrophobic polymer compound forming the composite polymer of the present invention is preferably copolymerized with a hydrophilic monomer in addition to the hydrophobic monomer. As such a hydrophilic monomer, Carboxyl group-containing monomers such as acrylic acid and methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate, alkylene oxide-containing monomers, acrylamides, methacrylamides, sulfonic acid group monomers, amino group-containing Monomers and the like can be preferably used,
It is particularly preferable to include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amide group-containing monomer, and a sulfone group-containing monomer. Since such a hydrophilic monomer is dissolved in water when added in a large amount, it is preferable to set the amount to about 0.1 to 30 wt%, and particularly preferably 1.0 to 20 wt%.
%. It is preferable to use a hydrophobic monomer having a glycidyl group as the hydrophobic monomer, at least 1.0 to 20 wt%, and particularly preferably 20 to 70 wt%.
%.

In the composite polymer of the present invention, by selecting the kind of the above-mentioned hydrophobic monomer and / or hydrophilic monomer, for example, a carboxyl group, a glycidyl group, an amino group, an amide group, an N-methylol group, etc. By using the hydrophobic monomer having a cross-linking group, a composite polymer having a cross-linking group can be obtained.

The composite polymer of the present invention preferably contains at least two copolymerizable ethylenically unsaturated monomers and is in the form of particles. Examples of such a monomer include those having two vinyl groups such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, and N, N-methylenebisacrylamide, and trivinyl. Those having three vinyl groups such as cyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol trimethacrylate, and vinyl groups such as pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.
Although the thing which has an individual can be mentioned, it is not limited to these.

When the composite polymer of the present invention is in the form of particles, the weight average particle diameter is particularly preferably 0.01 to 0.8 μm, and any weight average particle diameter of 0.005 to 3.0 μm can be used. Can also be preferably used.

The method for polymerizing the composite polymer of the present invention is as follows:
Examples thereof include emulsion polymerization method, solution polymerization method, bulk polymerization method, suspension polymerization method and radiation polymerization method.

In solution polymerization, a mixture of monomers having a suitable concentration in a solvent (usually 40% by weight or less, preferably 10 to 25% by weight, based on the solvent) is added in an amount of about 10% in the presence of an initiator. It can be obtained by carrying out the polymerization at a temperature of ˜200 ° C., preferably 30˜120 ° C. for about 0.5 to 48 hours, preferably 2 to 20 hours.

Any initiator may be used as long as it is soluble in a polymerization solvent, and examples thereof include benzoyl peroxide, azobisisobutyronitrile (AIBN), ditertiary butyl peroxide, and other organic solvent-based initiators, and peroxides. Water-soluble initiators such as ammonium sulfate (APS), potassium persulfate, and 2,2'-azobis- (2-amidinopropane) -hydrochloride, and a combination of these with a reducing agent such as Fe ²⁺ salt or sodium bisulfite. A redox type polymerization initiator etc. can be mentioned.

Any solvent can be used as long as it can dissolve a mixture of monomers, and examples thereof include water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, dioxane, and a mixed solvent of two or more of these. be able to. After completion of the polymerization, the reaction mixture can be separated and removed by pouring the reaction mixture into a medium in which the produced polymer is not dissolved, allowing the product to settle, and then drying.

In the emulsion polymerization method, water is used as the dispersion medium, and 10 to 50% by weight of the monomer relative to water and 0.0 relative to the monomer.
Using about 5 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant, about 30 to 100 ° C, preferably 60 to 90 ° C.
It is obtained by polymerizing under stirring for 3 to 8 hours.
The concentration of the monomer, the amount of the initiator, the reaction temperature, the time, etc. can be changed widely and easily.

Although a water-soluble polymer is used as the dispersant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used.

Examples of the water-soluble polymer as a dispersant include synthetic polymers and natural water-soluble polymers.
Any of these can be preferably used in the present invention. Among them, the synthetic water-soluble polymer, for example, those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, nonionic Examples thereof include those having a group and a cationic group, those having an anionic group and a cationic group, and the like. Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. As the anionic group,
Examples thereof include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include quaternary ammonium base and 3
Examples thereof include a primary amino group.

As the natural water-soluble polymer, for example, one having a nonionic group, one having an anionic group, one having a cationic group, one having a nonionic group and an anionic group in the molecular structure, Examples thereof include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like.

As the water-soluble polymer, whether it is a synthetic water-soluble polymer or a natural water-soluble polymer, those having an anionic group and those having a nonionic group and an anionic group can be preferably used.

In the present invention, the water-soluble polymer is 20
It may be dissolved in 0.05 g or more in 100 g of water at 0 ° C, and preferably 0.1 g or more.

When polymerizing the composite polymer of the present invention, it is preferable to allow a metal alkoxide compound to be present. Some metal alkoxide compounds are also called coupling agents, and various types such as silane coupling agents, titanium coupling agents, aluminum coupling agents, zirconium coupling agents are commercially available, but silane coupling agents are preferred. A ring agent and a titanium coupling agent.

The following are examples of these preferred compounds relating to the present invention.

[0037]

[Chemical 1]

[0038]

[Chemical 2]

[0039]

[Chemical 3]

[0040]

[Chemical 4]

The composite polymer of the present invention can be contained in the photographic constituent layer as it is or after being dissolved or dispersed in water. As the dispersion method, ultrasonic waves, a ball mill, an attritor, a pearl mill, a three-roll mill, a high speed grind device and the like can be preferably used.

The content of the polymer of the present invention is preferably 5 to 300% by weight, more preferably 10 to 150% by weight, based on the binder of the photographic component layer.

The place of addition may be a photosensitive layer or a non-photosensitive layer.

Next, an example of a method for producing the composite polymer of the present invention will be described.

(Production Method of Composite Polymer) Production Example 1 (Synthesis of PL-1) A 1,000 ml four-necked flask was provided with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing pipe, and a reflux condenser, and nitrogen was added. Distilled water 125cc, 20wt% while introducing gas and deoxidizing
225 g of antimony oxide sol was added and heated until the internal temperature reached 80 ° C. Surfactant S having the following structure as a dispersant
_{F-1 p-C 9 H} 19 - (C 6 H 4) -O (CH 2 CH 2 O) 6 (CH 2) 3 SO 3 Na 4.5g was added, ammonium persulfate 0.45g as further initiator Is added, and then 45 g of methyl methacrylate is added dropwise with a dropping funnel over about 1 hour. After the dropping was completed, the reaction was continued for 5 hours. Then, the mixture is cooled and adjusted to pH 6 with aqueous ammonia to obtain a composite polymer PL-1.

Production Example 2 (Synthesis of PL-3) A 1,000 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser, and nitrogen gas was introduced to deoxidize it. While distilled water 125cc, 10wt%
225 g of tin oxide sol was added and heated until the internal temperature reached 80 ° C. Further hydroxypropyl cellulose 4.5
g was added. Further, 0.45 g of ammonium persulfate is added as an initiator, and then 4 g of hydroxyethyl methacrylate and 16 g of methyl methacrylate are added dropwise with a dropping funnel over about 1 hour. After the dropping was completed, the reaction was continued for 4 hours, then cooled and adjusted to pH 6 with aqueous ammonia to obtain a composite polymer PL-3.

Specific examples of the composite polymer according to the present invention are shown below.

[0048]

[Chemical 5]

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

[Chemical 8]

Examples of the water-soluble polymer used in the hydrophilic colloid layer of the present invention include synthetic water-soluble polymers and natural water-soluble polymers, both of which are preferably used in the present invention. Among these, the synthetic water-soluble polymer includes, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure. Examples of the nonionic group include an ether group, ethylene oxide group, and hydroxy group, and examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like. Is mentioned.

These synthetic water-soluble polymers may be not only homopolymers but also copolymers with one or more monomers. Furthermore, the composition of the copolymer with the partially hydrophobic monomer is slightly restricted by the place of addition and the amount thereof, as long as the copolymer itself retains water solubility. That is, particularly when a large amount is added to the emulsion layer, it is necessary to limit the composition range so that side effects do not occur during the addition.

The natural water-soluble polymers include, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.

In the present invention, the water-soluble polymer may be dissolved in 100 g of water at 20 ° C. in an amount of 0.05 g or more, preferably 0.1 g or more.

Furthermore, it is preferable that the water-soluble polymer of the present invention has a higher solubility in a developing solution or a fixing solution, and the solubility is at least 0.05 g per 100 g of the developing solution.
It is preferably 0.5 g or more, and particularly preferably 1 g or more.

Examples of the synthetic water-soluble polymer include those containing the repeating unit of the following general formula [P] in an amount of 10 to 100 mol% in one molecule of the polymer.

[0058]

[Chemical 9]

In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent. For example, a methyl group. , Ethyl group, propyl group, butyl group, etc.), halogen atom (eg chlorine atom) or --CH ₂ COO
Represents M, L is -CONH-, -NHCO-, -COO-, -OCO
-, - CO -, - SO 2 -, - NHSO 2 -, - SO 2 NH- or -O
Represents-, J is an alkylene group, preferably 1 carbon atom
~ 10 alkylene groups (including those having a substituent are also included.
For example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, a hexylene group, etc., an arylene group (including those having a substituent, such as a phenylene group), and an aralkylene group (including those having a substituent are also included. ).

[0060]

[Chemical 10]

M represents a hydrogen atom or a cation group, and R
₉Is an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, etc.), R₃,
R_Four, R _Five, R₆, R₇And R₈Is the number of hydrogen atoms and carbon atoms
1-20 alkyl groups (eg methyl, ethyl,
Pill group, butyl group, hexyl group, decyl group, hexadecyl group
Group, etc.), alkenyl group (eg vinyl group, allyl group)
Etc.), phenyl group (eg, phenyl group, methoxyphenyl
Group, chlorophenyl group, etc.), aralkyl group (eg benzene)
Zyl group), X represents an anion, and p and
q represents 0 or 1, respectively. Especially acrylamide
Is preferably a polymer containing methacrylamide.

Y represents a hydrogen atom or-(L) _p- (J) _q- Q.

Further, the synthetic water-soluble monomer of the present invention can be copolymerized with an ethylenically unsaturated monomer. Examples of the copolymerizable ethylenically unsaturated monomer include styrene, alkylstyrene, hydroxyalkylstyrene (alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, butyl, etc.), vinylbenzenesulfonic acid and salts thereof, α-methylstyrene, 4-vinylpyridine, N
-Vinylpyrrolidone, monoethylenically unsaturated esters of fatty acids (eg vinyl acetate, vinyl propionate, etc.)
Ethylenically unsaturated monocarboxylic or dicarboxylic acids and salts thereof (eg acrylic acid, methacrylic acid) Maleic anhydride, esters of ethylenically unsaturated monocarboxylic acids or dicarboxylic acids (eg n-butyl acrylate, N, N- Diethylaminoethyl methacrylate, N, N-
Diethylaminoethyl methacrylate), amide of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (eg, acrylamide, sodium 2-acrylamido-2-methylpropanesulfonic acid, N, N-dimethyl-N'-methacryloylpropanediamineacetate betaine) And so on.

Next, specific examples of the synthetic water-soluble polymer represented by the general formula [P] will be given.

[0065]

[Chemical 11]

[0066]

[Chemical 12]

[0067]

[Chemical 13]

[0068]

[Chemical 14]

[0069]

[Chemical 15]

[0070]

[Chemical 16]

The number average molecular weight of the synthetic water-soluble polymer of the present invention is 20,000 or less. It is preferably 10,000 or less. or,
More preferably, it is 5000 or less.

As the natural water-soluble polymer, it is described in detail in the collection of technical data on water-soluble polymer water-dispersible resin (published by the Management Development Center). Lignin, starch, pullulan, cellulose, alginic acid, dextran, Dextrin, guar gum, gum arabic, pectin, casein, agar, xanthan gum, cyclodextrin, locust bean gum, tragacanth gum, carrageenan,
Glycogen, laminaran, lichenin, nigeran and the like, and derivatives thereof are preferred.

As the natural water-soluble polymer derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, or carboxyalkylenated, alkylphosphorylated, and salts thereof, polyoxyalkylenes (eg, ethylene, glycerin, Propylene, etc.),
Alkylation (methyl, ethyl, benzylation, etc.) is preferred.

In the present invention, the natural water-soluble polymer is 2
You may use it in combination of 2 or more types.

Among the natural water-soluble polymers, glucose polymer and its derivative are preferable, and among glucose polymer and its derivative, starch, glycogen,
Cellulose, lichenin, dextran, dextrin,
Cyclodextrin, nigeran and the like are preferable, and dextrin, cyclodextrin and derivatives thereof are particularly preferable.

The number average molecular weight of these natural water-soluble polymers is preferably 20,000 or less, and particularly preferably 10,000 or less. Further, it is more preferably 5000 or less. The addition amount of the synthetic or natural water-soluble polymer used in the present invention is preferably 0.01 to ² g / m ² , more preferably 0.05 to 1 g / m ² . More preferably 0.1 to
It is 0.5 g / m ² . The layer to be added is preferably an emulsion layer, but may be added in a necessary amount to other hydrophilic colloid layers if necessary.

The synthetic or natural water-soluble polymer used in the present invention may be used alone, or if necessary, two or more kinds may be used in combination.

The synthetic or natural water-soluble polymer used in the present invention is contained in the photographic light-sensitive material in an amount of 10% or more, preferably 10% or more and 30% or less, based on the total weight of the photographic material.

The dextrin used in the present invention is α-
It is a polymer of 1,4-bonded D-glucose, and generally refers to a general term for various degradation products from hydrolysis of starch to maltose. It has no particular structural characteristics, and its molecular weight is not constant, except that some are structurally important as academically important. There are many types, depending on the method and application of hydrolysis, from high molecular weight ones obtained by slightly hydrolyzing starch to low molecular weight ones which do not exhibit iodine starch reaction.

Specific examples of dextrins are trade names such as LLD from Meito Sangyo Co., Ltd., trade names such as Amycor 1 and Dextrin 102S from Nitto Kagaku Co., Ltd.
In addition, those commercially available from Towa Kasei Kogyo Co., Ltd. under the trade name of PEO and the like can be mentioned.

In the present invention, it is preferable to use a polymer latex generally used in silver halide photographic light-sensitive materials. That is, it is a polymerizable ethylene-based compound or a polymerizable diolefin-based compound and is roughly classified into a hydrophobic monomer and a hydrophilic monomer. Examples of the hydrophobic monomer include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate. , 2-ethylhexyl methacrylate, t-butyl methacrylate, is
alkyl methacrylates such as o-propyl methacrylate, glycidyl acrylate, glycidyl esters such as glycidyl methacrylate, alkenylbenzenes such as styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, vinyl acetate, vinyl propionate, etc. Vinyl ethers, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and phenyl vinyl ether, vinyl halides such as vinyl chloride, vinyl bromide and vinylidene chloride, acrylic acid amide,
Examples thereof include amides such as methacrylic acid amide and diene monomers such as butadiene. In addition, as the hydrophilic monomer, hydroxyethyl acrylate, hydroxyalkyl acrylate such as hydroxypropyl acrylate, methacrylic acid hydroxyalkyl ester such as hydroxyethyl methacrylate and hydroxypropyl methacrylate, tetraethylene glycol,
(Meth) acrylic acid ethylene glycols such as monomethacrylate, acrylic acid, methacrylic acid, itaconic acid,
Examples thereof include ionic monomers such as α-acrylamido-2-methylpropanesulfonic acid. These monomers may be used alone or in combination of two or more kinds, but when a hydrophilic monomer is used, it is preferable to use it in combination with a hydrophobic monomer to obtain a stable latex. In order to obtain it, it is better not to use hydrophilic monomers so much.

The polymer latex used in the present invention may be obtained from the beginning by an emulsion polymerization method or a suspension polymerization method in which a polymer is polymerized in a dispersion medium. Alternatively, the polymer latex may be separately polymerized and taken out.
This may be redispersed to obtain a polymer latex, but the emulsion polymerization method is preferable in terms of production cost, dispersion stability and the like.

In the present invention, a polymer latex which is particularly preferably used is JP-A-6-266035.
The epoxy ring-opening rate described in No. 35 is 35 mol% or more, and a latex having a glycidyl acrylate unit can be used.

The index of Tg (glass transition point) is often used for latex, and its determination is not simple, but in the present invention, considering photographic performance and physical properties, -2.
It is preferably 0 ° C or higher.

In the present invention, the amount of gelatin in the total hydrophilic colloid layer including the emulsion layer on one side of the support is 1.0-2.
0 g / m ² is preferable, and 1.3 to 1.
It is 8 g / m ² . Examples of gelatin used include so-called alkali-processed gelatin and acid-processed gelatin.

In the present invention, it is preferable that the non-photosensitive hydrophilic colloid layer coated as the outermost layer contains an antistatic agent.

As the antistatic agent, generally used surfactants and hydrophilic polymers are also preferably used. As the surfactant, nonionic surfactants, anionic surfactants, cationic surfactants, betaine surfactants, and fluorine-based surfactants are often used. Further, as the hydrophilic polymer,
Nonionic, cationic, and anionic polymers are often used.

In the present invention, in addition to the above antistatic agent, conductive metal fine particles such as tin oxide and alumina sol are also preferably used. Specific examples of the antistatic agent preferably used in the present invention include, for example, Japanese Patent Application No. 7-643.
Those described in No. 27 are mentioned.

Next, the silver halide grains used in the present invention will be described.

The silver halide grains used in the present invention are not particularly limited, but tabular silver halide grains having an aspect ratio of 2 or more are preferable. More preferably, it is 2.0 or more and less than 15.0. It is particularly preferably 4 or more and less than 8.

As the silver halide used in the present invention, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide or the like can be used as the silver halide. The silver iodide content is preferably 1.0 mol% or less, more preferably 0.5 mol% or less, as the average silver iodide content in the entire silver halide grains.

In the present invention, the silver halide grains may have various halogen compositions, but it is preferable that the silver halide grains contain silver chloride in an amount of 50 mol% or more, more preferably 70 mol% or more.

The tabular silver halide grains used in the present invention can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to nucleate with low pCl in the presence of iodide ions under the condition that the (100) plane is easily formed. After nucleation, Ostwald ripening and / or growth can be performed to obtain tabular silver halide grains having a desired grain size and distribution. The tabular silver halide grains used in the present invention may be so-called halogen conversion type grains. The amount of halogen conversion is preferably 0.2 mol% to 0.5 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after physical ripening.

The silver halide grains are cadmium salt, zinc salt,
Lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt), ruthenium salt (including complex salt),
It is preferable to add a metal ion using at least one selected from an osmium salt (including a complex salt) and an iron salt (including a complex salt) so that these metal elements are contained inside and / or on the surface of the particle.

In the present invention, it is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is added in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol / mol of silver.
It is preferable to add ^-2 mol or less.

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains. As the gelatin, alkali-processed gelatin, acid-processed gelatin, low molecular weight gelatin (molecular weight of 20,000 to 10) is used.
10,000), modified gelatin such as phthalated gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure (Resea)
rch Disclosure. Hereinafter abbreviated as RD) First
Volume 76 No. 17643 (December 1978).

In the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be contained. In the case of removing the salts, RD Vol. It can be performed based on the method described in Section II of 17643.

The silver halide grains of the present invention can be chemically sensitized. Chemical ripening or chemical sensitization process conditions,
For example, pH, pAg, temperature, time and the like are not particularly limited, and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitizing method using a selenium compound, a tellurium sensitizing method using a tellurium compound, and a reducing substance are used. The reduction sensitization method, gold or other, a noble metal sensitization method using a noble metal or the like can be used alone or in combination, and among them, a selenium sensitization method, a tellurium sensitization method, a reduction sensitization method and the like are preferably used.
Particularly, the selenium sensitization method is preferably used.

Silver nitrate is preferred as the water-soluble silver salt. So-called silver ripening, which is one of reduction sensitization techniques, is performed by adding a water-soluble silver salt. The pAg during silver ripening is suitably 1 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but the stabilizer disclosed in JP-A-57-82831 is used. Inhibitor and / or V.I. S. Paper by Gahler [Zeitshift fur wissens
chaftriche Photographie B
d. 63, 133 (1969)] and JP-A-54-1.
Good results are often obtained in combination with the thiosulphonic acids described in 019. The addition of these compounds may be carried out at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

The silver halide grain according to the present invention may be spectrally sensitized with a methine dye or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobola cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

These dyes can be applied to any of the commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc., and a nucleus in which an aliphatic hydrocarbon ring is fused to these nuclei, that is, India A renin nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization. Further, together with the sensitizing dye, a dye having no spectral sensitizing property or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect may be contained in the emulsion layer. For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
33,390, 3,635,721), aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,510), cadmium salt, azaindene compound, etc. Good.

The sensitizing dye may be added during or during each step of nucleation, growth, desalting, chemical sensitization, or after chemical sensitization.

Next, the effect of the present invention can be further enhanced by adding inorganic fine particles having a particle diameter of 1 to 300 nm to any layer (especially emulsion layer) in the photographic light-sensitive material. The inorganic fine particles having a particle size of 1 to 300 nm are mainly composed of silicon, aluminum, titanium, indium, yttrium, tin, antimony, zinc, nickel, copper,
An oxide selected from iron, cobalt, manganese, molybdenum, niobium, zirconium, vanadium, alkali metals, alkaline earth metals and the like, among which transparency,
From the viewpoint of hardness, silicon oxide (colloidal silica), aluminum oxide, antimony oxide, titanium oxide, zinc oxide, zirconium oxide, tin oxide, vanadium oxide, and yttrium oxide are preferable. When these inorganic oxides are dispersed in water to form a sol, the surface thereof may be treated with alumina, yttrium, cerium or the like in order to enhance the water dispersion stability of itself. It may be shelled with pre-crosslinked gelatin in order to enhance the affinity with gelatin. The amount of the inorganic fine particles used in the present invention is preferably 0.05 to 1.0 by dry weight ratio, and particularly preferably 0.1 to 0. 0, based on gelatin used as the binder of the layer to be added. 7
Is. The above-mentioned inorganic fine particles may be used in combination.

In the present invention, the matting agent is a homopolymer of polymethylmethacrylate or a polymer of methylmethacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, strontium sulfate, and barium sulfate. Can be used together. The particle size is 0.6-10μ
m, particularly preferably 1 to 5 μm.

In the surface layer of the silver halide photographic light-sensitive material of the present invention, a paraffin wax, a higher fatty acid ester, a silicone compound and colloidal silica are used as a slip agent.
A starch derivative or the like can be used.

The constituent layers of the silver halide photographic light-sensitive material of the present invention include trimethylolpropane, pentanediol,
Polyols such as butanediol, ethylene glycol and glycerin can be added as plasticizers.

When the silver halide photographic light-sensitive material of the present invention is used as a medical double-sided emulsion X-ray light-sensitive material, it is preferable to provide a transverse light-blocking layer for the purpose of improving image sharpness. The transverse light blocking layer contains a solid fine particle dispersion of a dye for the purpose of absorbing transverse light. Such a dye is not particularly limited as long as it is a dye that is soluble in an alkali having a pH of 9 or more and hardly soluble at a pH of 7 or less, but it is excellent in decolorizing property during development processing. The compound of the general formula (1) described in -308670 is preferably used.

Preferred developing solutions for developing the silver halide light-sensitive material of the present invention include dihydroxybenzenes such as hydroquinone and para-aminophenols such as p-aminophenol and N-methyl-p- as developing agents.
Aminophenol, 2,4-diaminophenol, etc.
Examples of 3-pyrazolidones include 1-phenyl-3
-Pyrazolidones, 1-phenyl-3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone, 5,5-dimethyl-1-phenyl-3
-Pyrazolidone and the like are preferably used in combination.

The above-mentioned para-aminophenols, 3-
The amount of aminopyrazolidones used is preferably 0.004 mol / liter, more preferably 0.04 to 0.1.
It is 2 mol / liter.

Further, the total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones contained in the components of all the development processing solutions is preferably 0.1 mol / liter or less.

The preservative may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / liter, more preferably 0.3 to 0.6 mol / liter. Further, addition of a large amount of ascorbic acid also leads to processing stability.

As the alkaline agent, sodium hydroxide,
Includes pH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate. Further, a buffering agent such as sucrose, acetoxime, 5-sulfosalicylic acid, phosphate or carbonate may be used. The content of these agents is such that the pH of the developer is 9.0 to
13, preferably chosen to have a pH of 10 to 12.5.

As the solubilizing agent, polyethylene glycols and their esters, and as the sensitizing agent,
For example, a development accelerator, a surfactant, etc. such as a quaternary ammonium salt can be contained.

As the silver sludge inhibitor, sulfide,
Disulfide compounds, cysteine derivatives or triazine compounds are preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, imidazole type, benzimidazole type, triazole type, benztriazole type, tetrazole type or thiadiazole type compound is used.

Examples of the inorganic inhibitor include sodium bromide, potassium bromide, potassium iodide and the like. Besides this,
L. F. A. Menson's "Photographic Processing Chemistry" published by Focal Press (19
66) 226-229, U.S. Pat. No. 2,193,0
No. 15, 2,592,364, JP-A-48-649.
Those described in No. 33 and the like may be used. As a chelating agent for concealing calcium ions mixed in tap water used as a treatment liquid, an organic chelating agent is disclosed in Japanese Patent Laid-Open No.
The chelating stability constant with iron described in -193853 is 8
The above chelating agents are preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the development hardening agent, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

The replenishment in the present invention replenishes the amount corresponding to processing fatigue and oxidation fatigue, and the replenishment amount is 35 per m ^{2 of} the photographic light-sensitive material.
Do a replenishment rate of ~ 98 ml. As a supplement method,
Replenishment by width and feed speed described in JP-A-55-126243, area supplementation described in JP-A-60-104946,
Area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156 may be used.

Preferred fixing solutions can include fixing materials commonly used in the art. pH 3.
It is 8 or more, preferably 4.2 to 5.5.

As a fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferable in terms of fixing speed. The concentration of ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably 0.8 to 3 mol / l.

The fixing solution of the present invention may be one which performs acid hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferably added in the form of aluminum sulfate, aluminum chloride, potassium alum, or the like.

Others In the fixing solution of the present invention, if desired, preservatives such as sulfite and bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid) and organic acids (citric acid, oxalic acid). ,
Malic acid, etc.), various acids such as hydrochloric acid, pH adjusting agents such as metal hydroxides (potassium hydroxide, sodium), and chelating agents having the ability to soften water.

As the fixing accelerator, for example, Japanese Patent Publication No. 45-
No. 35754, No. 58-122535, No. 58-12.
2536, thiourea derivative, US Pat. No. 4,12
Examples thereof include thioethers described in No. 6,459.

The silver halide emulsion layer of the present invention preferably has a swelling ratio during development of 150 to 250% and a film thickness after expansion of 70 μm or less. Water swelling rate is 250%
If it exceeds the above range, poor drying occurs, and, for example, defective transport occurs in automatic processor processing, especially in rapid processing. Further, if the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling rate is the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing,
This is divided by the film thickness before processing and multiplied by 100.

The silver halide photographic light-sensitive material of the present invention exhibits excellent performance in rapid development processing by an automatic processor having a total processing time of 10 to 25 seconds. In the rapid processing of the present invention, the temperature and time for developing, fixing and the like are about 25 ° C. to 50 ° C. and 15 seconds or less, respectively, but preferably 30 ° C. to 40 ° C. and 2 seconds to 10 seconds. In the present invention, the silver halide photographic light-sensitive material is washed with water after being developed and fixed. Here, in the water washing step, a water-saving treatment can be performed by using a countercurrent water washing method of two or three stages. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. The temperature and time of the water washing process are 5 ° C to 50 ° C and 2
Seconds to 10 seconds are preferred. In the present invention, the photographic light-sensitive material which has been developed, fixed and washed with water is dried through a squeeze roller. As the drying method, either hot air convection drying, radiant drying with a far infrared heater, heat transfer drying with a heat roller, or a combination thereof can be used. Drying temperature and time is 40 ℃
It is carried out at -100 ° C for 4-15 seconds. The total processing time in the present invention means that after the tip of the film is inserted into the insertion port of the automatic developing machine, the developing tank, the transition portion, the fixing tank, the transition portion,
It is the total time from the passage through the washing tank, the transition portion, and the drying portion until the leading edge of the film emerges from the drying outlet. Since the silver halide photographic light-sensitive material of the present invention can reduce the amount of gelatin used as the binder of the emulsion layer and the protective layer without impairing the pressure characteristics, the total processing time is 10
Even in the rapid processing of up to 25 seconds, the developing processing can be carried out without impairing the developing speed, the fixing speed and the drying speed.

[0127]

The present invention will be described with reference to the following examples.

Example 1 The method for preparing the emulsion is shown below.

(Preparation of Em-1) A tabular silver iodochloride emulsion Em-1 was prepared using the following 5 kinds of solutions.

A1 Low methionine gelatin 214.37 g Sodium chloride 1.995 g Potassium iodide 149.6 mg Water to make 6090 ml B1 Sodium chloride 10.48 g Potassium iodide 149.4 g Water to make 90 ml C1 Silver nitrate 30.58 g Water Finish to 90 ml D1 Sodium chloride 165.0 g Finish to 5640 ml with water E1 Silver nitrate 479.0 g Finish to 5640 ml with water Stir solution A1 vigorously in the reaction vessel while keeping it at 40 ° C., and add all the amounts of solution B1 and solution C1 there. 180 ml per minute
Was added by the simultaneous mixing method at a flow rate of 30 seconds. next,
After keeping this mixed solution at 40 ° C. for 10 minutes, the solution D1 and the solution E1 were added by the simultaneous mixing method at a flow rate of 24 ml per minute over 40 minutes, and then the remaining total amount of the solution D1 and the solution E1 was further initialized. The flow rate was linearly increased so that the flow rate was 24 ml and the final flow rate was 48 ml, and the addition was performed by the simultaneous addition method over 130 minutes. During this time, pCl was kept at 2.35 throughout. After that, adjust to 1.30 with sodium chloride,
The pCl was adjusted to 2.0 using an ultrafiltration membrane, and sodium chloride was further added to adjust the pCl to 1.65.

The obtained silver halide emulsion has an iodide of 0.0
6 mol% contained, and when observed by an electron microscope, the average particle size (converted to a circle diameter) is 1.45 μm, and the average thickness is 0.13 μ
m, average aspect ratio 11, diameter variation coefficient 18.5%
Was a monodisperse tabular silver halide grain whose main plane was square (adjacent edge ratio: 1.4).

Subsequently, the above-mentioned emulsion Em-1 was divided into predetermined amounts and heated to 55 ° C., and then the predetermined amounts of the following spectral sensitizing dyes (A) and (B) were added as solid fine particle dispersions. Ammonium thiocyanate, chloroauric acid aqueous solution,
An aqueous solution or methanol solution of a sulfur sensitizer and a solid fine particle dispersion of triphenylphosphine selenide shown below were added, and aging was carried out for a total of 2 hours. 4-hydroxy-6-methyl-1,3,3 as a stabilizer at the end of aging
a, 7-Tetrazaindene (TAI) was added.

The additives and their addition amounts (per mol of AgX) are shown below.

Spectral sensitizing dye (A) 300 mg Spectral sensitizing dye (B) 375 mg Ammonium thiocyanate 145 mg Chloroauric acid 18.5 mg Sodium thiosulfate (pentahydrate) 15.0 mg 1-Ethyl-3- (2-thiazolyl) ) Thiourea 3.8 mg Elemental sulfur 3.5 mg Triphenylphosphine selenide 3.0 mg Stabilizer (TAI) 1000 mg Solid fine particle dispersion of spectral sensitizing dye is disclosed in JP-A-5-297.
It was prepared by a method similar to the method described in No. 496.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was previously adjusted to 27 ° C., and the mixture was mixed with a high-speed stirrer (dissolver) for 3,5.
Obtained by stirring at 00 rpm for 30-120 minutes.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine-sodium salt anhydride sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl- 3,3′-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride The following coating liquid was added to glycidyl methacrylate 50 wt%,
The concentration of the copolymer composed of 3 kinds of monomers of 10 wt% methyl acrylate and 40 wt% butyl methacrylate is 1
The copolymer aqueous dispersion obtained by diluting so as to have a concentration of 0 wt% was subjected to an undercoating treatment using a blue concentration of 0.1.
A 175 .mu.m thick polyethylene terephthalate support colored 5 was coated on both sides with a transverse light-shielding layer, an emulsion layer, a protective lower layer and a protective upper layer in this order at a speed of 150 m / min and dried.

The following numerical values show the amount added per m ² .

(Preparation of sample) First layer (transverse light shielding layer)     Solid fine particle dispersion dye (AH) 50 mg     Gelatin 0.1g     Sodium dodecylbenzene sulfonate 5mg     Compound (I) 5 mg     2,4-dichloro-6-hydroxy-1,3,5-       Triazine sodium salt 5mg     Colloidal silica (average particle size 0.014 μm) 10 mg     Latex (L) 0.2g     Polystyrene potassium sulfonate 50mg Second layer (emulsion layer) The following various additives were added to the emulsion obtained above.

Potassium tetrachloropalladium (2) acid 100 mg Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 130 mg Polyvinylpyrrolidone ( Molecular weight 10,000) 35 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 50 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 20 mg 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 100 mg 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 5mg compound _{(H) 0.5mg n-C 4} H 9 OCH 2 CH (OH) CH 2 n (CH 2 COOH) 2 35mg of compound (M) 5mg compound ( N) 5 mg Complex polymer of the present invention Amount shown in Table 2 Colloidal silica (average particle size 0.014 μm) 25 mg Latex (L) 25 mg Water-soluble polymer of the present invention Amount shown in Table 2 However, the amount of gelatin is shown in Table 2. The amount was adjusted.

Third layer (lower protective layer) Gelatin 0.2 g Latex (L) 0.1 g Sodium polyacrylate (average molecular weight 500000) 30 mg Compound (K) 15 mg Fourth layer (upper protective layer) Gelatin 0.4 g Antistatic agent (AP) 0.2 g 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 50 mg Polymethylmethacrylate particles (average particle size 4.0 μm) 20 mg Polymethylmethacrylate particles (average particle size 1.0 μm ) 50 mg colloidal silica (average particle size 0.014 μm) 10 mg formaldehyde 20 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg bis-vinylsulfonylmethyl ether 36 mg polyacrylamide (average molecular weight 10000) 50mg policy Xanthane (SI) 20 mg Compound (I) 12 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound (O) 50 mg Compound (S-2) 5 mg Compound (F-1) 3 mg Compound (F-2) 2 mg Compound ( F-3) 1 mg The amount of material applied was for one side, and the coated silver amount was adjusted to be 1.0 g / m ² for one side.

[0141]

[Chemical 17]

[0142]

[Chemical 18]

(1) Evaluation of Sensitivity The coated and dried sample was stored at 23 ° C. and 55% RH for 3 days, then pinched with an intensifying screen KO-250 for X-ray photography, and irradiated with X-rays through a penetrometer B type. Processing was performed using a roller-conveying type automatic developing machine (SRX-501: manufactured by Konica Corporation) with a developing solution and a fixing solution having the following compositions.

[0144] Developer formulation Part-A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 340 g Add water to finish to 5000 ml Part-B (for 12 l finishing) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter glacial acetic acid 120 g Potassium bromide 225 g Fixer formulation to add water to finish 1.0 liter Part-A (for 18 liter finish) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate Trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulphate 800 g To prepare a developing solution, Part A and Part B are simultaneously added to about 5 l of water. Water was added while stirring and dissolving, and the resulting solution was adjusted to 12 l with glacial acetic acid, and the pH was adjusted to 10.40. This is used as a development replenisher.

20 ml / l of the aforesaid starter was added to 1 liter of this development replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A, P to about 5 liters of water.
ArtB is added simultaneously, and water is added while stirring and dissolving.
The pH was adjusted to 4.4 with sulfuric acid and NaOH. This is the fixing replenisher.

The sensitivity was expressed as a relative value with the reciprocal of the exposure energy amount required for the sample 1 to give a density of fog +1.0 as 100.

(2) Fog evaluation temperature 23 ° C., 50% RH condition (A), temperature 55 ° C.,
Each sample was stored for 5 days under the condition (B) of 50% RH, and then subjected to the same development treatment as the above (1) without exposing. The density of each sample was measured, and the fog density difference Δfog was obtained by subtracting the value of the sample stored under the condition (A) from the value of the sample stored under the condition (B).

(3) Evaluation of pressure resistance The obtained sample was allowed to stand at 23 ° C. and 40% RH for 2 hours, and then continuously loaded scratch tester (HEIDO manufactured by Shinto Scientific Co., Ltd.).
(N-18 type), after rubbing the surface of the sample with a continuous load of 0 to 200 g with a sapphire needle having a diameter of 0.1 mm, the same development processing as in the above (1) is performed without exposing, and the blackening density is fogging. The load to obtain +0.1 was obtained. That is, the larger this value, the better the pressure resistance.

(4) Evaluation of cracks The obtained sample was cut out into a size of 35 mm × 135 mm, placed in a container filled with silica gel without being exposed to light and sealed, and kept in an absolutely dry state (˜0% RH) at 45 ° C. for 14 days. After storage, the same development processing as described above was performed, and the presence or absence of cracks (having a length of 1 mm or more) in the stored sample was evaluated.
It should be noted that under the above storage conditions, it is necessary that even one crack does not occur.

Evaluation ◯: No occurrence X: Occurrence (5) Evaluation of roller mark The sample was uniformly exposed in a size of 10 × 12 inches so that the blackening density was 1.0, and then the above treatment was performed. The developing rack used at this time and the transfer rack from developing to fixing were intentionally fatigued. That is, since the rollers of each rack were fatigued, unevenness of about 10 μm was formed on the entire surface. Due to the pressure caused by the unevenness in the processed sample, many fine spot-like density unevenness occurred in the sample having poor pressure resistance. This level was visually evaluated by the following ranks.

5: No spots are generated 4: Slight spots are generated, but this is not a problem for practical use Level 3: A small amount of spots are generated, but an allowable limit level that is not generated in a normal rack Level 2: Spots are generated It usually occurs on racks as well: 1: spots occur frequently. Tables 2 and 3 show the results that are always generated even in the normal rack.

[0153]

[Table 2]

As is apparent from Table 2, according to the present invention, a silver halide photographic light-sensitive material having high sensitivity and excellent pressure resistance and free from cracks can be obtained.

Example 2 Sample No. prepared in Example 1 1 to 15 were exposed to X-rays, the developing solution and fixing solution of Example 1 were used, and the automatic developing machine was modified from SRX-501 (manufactured by Konica Corporation) used in Example 1 to convey speed. Each of the samples was treated under the following conditions until the running equilibrium was reached, and a running equilibrium solution 1, a running equilibrium solution 2, and a running equilibrium solution 3 were prepared.

Processing conditions Temperature (° C.) Time (sec) Development 38 7.0 Fixing 37 4.0 Washing with water 26 7.0 Squeeze 2.4 Drying 58 4.0 Total (Dry To Dry) 24.4 seconds Replenishment condition ( Running equilibrium solution 1 Running equilibrium solution 2 Running equilibrium solution 3 Development replenishment amount 14.0 7.0 3.5 (180 ml / m ² ) (90 ml / m ² ) (45 ml / m ² ) Fixing replenishment amount 14.0 7.0 3.5 (180 ml / m ² ) (90 ml / m ² ) (45 ml / m ² ) Sample No. prepared in Example 1 1 to 15 were treated under the above conditions using the above running equilibrium liquid 1 (condition 1), running equilibrium liquid 2 (condition 2) and running equilibrium liquid 3 (condition 3) to evaluate sensitivity and roller mark. went.

[0157]

[Table 3]

As is clear from Table 3, according to the present invention, it is possible to obtain a photographic light-sensitive material excellent in pressure characteristics with a small decrease in sensitivity even with ultra-rapid processing with a low replenishing amount.

[0159]

EFFECTS OF THE INVENTION According to the present invention, a halogen having high sensitivity and excellent pressure resistance even at a treatment with a low replenishment rate, and having no film cracking at low humidity and being suitable for ultra-rapid treatment with less deterioration of fog. A silver halide photographic light-sensitive material and a processing method thereof were obtained.

Front page continuation (51) Int.Cl. ⁷ identification code FI G03C 5/31 G03C 5/31 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/06 501 G03C 1/04-1 / 04 501 G03C 1/047 G03C 1/32

Claims (4)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer, wherein at least one metal oxide grain is contained in at least one of the silver halide emulsion layers. And a composite polymer composed of a hydrophobic polymer and containing the silver halide emulsion layer and / or
Alternatively, at least one non-photosensitive hydrophilic colloid layer contains dextrin or cyclodextrin having a number average molecular weight of 20,000 or less.
A silver halide photographic light-sensitive material containing a water-soluble polymer selected from the group consisting of amines and derivatives thereof , wherein the hydrophobic polymer has at least an ester group having 6 or more carbon atoms.
A silver halide comprising a monomer selected from acrylic acid esters or methacrylic acid esters and a monomer selected from acrylic acid esters having a glycidyl group or methacrylic acid esters having a glycidyl group. Photographic material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the water-soluble polymer is dextrin. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the amount of gelatin in the total hydrophilic colloid layer on one side of the support is 1.0 to 2.0 g / m ^2. material. 4. The total processing time of the silver halide photographic light-sensitive material according to any one of claims 1 to 3 with a development replenisher of 35 to 98 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. A method for processing a silver halide photographic light-sensitive material, which comprises processing with an automatic processor for 10 to 25 seconds.