JPH0693088B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material and a superhigh contrast negative image forming method using the same, and particularly to a silver halide photographic used in a photomechanical process. It relates to a photosensitive material.

(Conventional technology and its problems) In the fields of graphics and arts, ultra-high contrast (especially gamma of 10 or more) photographs in order to achieve good reproduction of continuous tone images or halftone images by halftone dot images. What is needed is an imaging system that exhibits characteristics.

As a method of obtaining a high-contrast photographic property using a stable developing solution, U.S. Patent Nos. 4,224,401 and 4,168,977.
No. 4,166,742, 4,311,781, 4,272,60
Methods using hydrazine derivatives described in No. 6, No. 4,221,857, No. 4,269,929, etc. are known.
According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against air oxidation is not improved in the lith developer. Greatly improved compared to.

Further, for a low-sensitivity bright room light-sensitive material containing a hydrazine derivative which is widely used in the returning step during the photolithography process,
JP-A-60-14038, JP-A-60-162246, JP-A-61-238049
No. 62-65116, Japanese Patent Application No. 62-18648, 62-43704
No., etc.

On the other hand, due to the variety and complexity of printed matter, the photolithography process is often a more complicated process, and improvements such as rationalization of work and labor saving are required. In particular, when line drawing / half-tone photography is performed using a super-high-contrast sensitive material, or when contact back exposure is performed, electrostatic friction accumulates due to contact friction or peeling between the surfaces of photosensitive materials or different substances. It is said that the dust randomly attached to the photosensitive material or the original film causes the traces to remain as pinholes after the development processing, and it is necessary to spend a great deal of effort to correct or redo the exposure. There was a problem. In order to improve such problems, a technique for improving the charging property of a photosensitive material by using a surfactant has been introduced, but it is still not sufficient, and the charging property is lost particularly by developing. However, when this film is used as a document, there is a defect that the pinhole is hardly improved.

Further, in the plate making process that requires reproduction of halftone images and precise line drawings for multicolor printing, the dimensional change of the photographic light-sensitive material due to expansion and contraction of the hydrophilic colloid layer is a very serious drawback. Become.

Various means have been known for improving the dimensional stability of silver halide photographic light-sensitive materials.

For example, in U.S. Pat.No. 3,201,250, a technique for defining the thickness ratio between the hydrocolloid layer and the support, Japanese Patent Publication No. 39-4272,
39-17702, 43-13482, 45-5331, U.S. Patent 2
37,600, 2,763,625, 2,772,166, 2,852,38
No. 6, No. 2,853,457, No. 3,397,988, No. 3,411,911,
No. 3,411,912 describes a method of adding a polymer latex into a hydrocolloid photographic layer.

It is certainly possible to improve the dimensional change of the silver halide photographic light-sensitive material by changing the temperature and humidity by using these techniques.

However, these techniques cannot prevent the dimensional change due to the development processing of the silver halide photographic light-sensitive material. The phenomenon of dimensional change accompanying the development processing is a phenomenon that the dimension of the silver halide photographic light-sensitive material changes due to the development processing, and the dimension changes during exposure and after development. This is a very serious drawback in using the light-sensitive material.

To improve the dimensional stability associated with this development processing,
62-94133 describes the technique of using a vinylidene chloride undercoat.

However, even if this technique is used, it is not possible to safely improve the dimensional stability associated with the development processing.

In silver halide photographic light-sensitive materials exhibiting ultra-high contrast photographic properties, these drawbacks are important issues for streamlining work in the plate making process, saving labor, and improving the quality of printed matter. There has been a strong demand for the development of a silver halide photographic light-sensitive material that rarely occurs and has a small dimensional change.

(Object of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having a very high contrast of γ of more than 10 and having few pinholes and good dimensional stability by using a stable developing solution. To do.

(Structure of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the constituent layers of the silver halide photographic light-sensitive material is When the surface resistivity is 10 ¹² Ω or less in an atmosphere of 25 ° C. and 25% RH, and a silver halide emulsion layer and other hydrophilic colloid layer coating solution are applied and dried on the support, Based on the dry weight of the binder contained in all the layers constructed above, moisture of 300% or less is dried at a relative humidity of 50% or less, and after drying, the silver halide photographic light-sensitive material is subjected to absolute humidity and 1%. It was achieved by subjecting the silver halide photographic light-sensitive material to heat treatment in the following atmosphere at a temperature of 30 ° C. or higher for 6 hours or longer, and storing the silver halide photographic light-sensitive material in an atmosphere of absolute humidity of 1% or lower.

As the conductive substance used in the conductive layer of the present invention, a conductive metal oxide, a conductive polymer compound, or the like is used.

Crystalline metal oxide particles are preferable as the conductive metal oxide used in the present invention, but those containing oxygen vacancies and those containing a small amount of foreign atoms forming a donor with respect to the metal oxide used. Generally, it is particularly preferable because it has high conductivity, and the latter is particularly preferable because it does not cause fog in the silver halide emulsion. Examples of metal oxides are ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, Ba.
O, MoO ₃ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. As an example containing a heteroatom, for example, addition of Al, In, etc. to ZnO, S
For nO ₂ , addition of Sb, Nb, halogen elements, etc.
_{For 2} , the addition of Nb, Ta, etc. is effective. The addition amount of these heteroatoms is preferably in the range of 0.01 mol% to 30 mol%, and particularly preferably 0.1 mol% to 10 mol%.

The metal oxide fine particles of the present invention have conductivity, and their volume resistivity is preferably 10 ⁷ Ω-cm or less, and particularly preferably 10 ⁵ Ω-cm or less.

Regarding these oxides, JP-A-56-143431 and JP-A-56-12
0519, 58-62647, etc.

Further, as described in JP-B-59-6235, other crystalline metal oxide particles or a fibrous material (for example, titanium oxide) to which the above metal oxide is attached may be used as a conductive material.

The particle size that can be used is preferably 10 μm or less, but when it is 2 μm or less, stability after dispersion is good and it is easy to use. Further, in order to make the light scattering property as small as possible, it is very preferable to use conductive particles of 0.5 μm or less because a transparent photosensitive material can be formed.

When the conductive material is needle-like or fibrous, the length is preferably 30 μm or less and the diameter is 2 μm or less, and particularly preferably, the length is 25 μm or less and the diameter is 0.5 μm or less.
The diameter ratio is 3 or more.

Examples of the conductive polymer compound used in the present invention include polyvinylbenzene sulfonates, polyvinylbenzyltrimethylammonium chloride, and US Pat.
8,802, 4,118,231, 4,126,467, 4,137,217
Quaternary salt polymers described in U.S. Pat. No. 4,070,189
No. 2, OLS 2,830,767, JP-A 61-296352, 61-62033
Polymer latexes and the like described in JP-A-No.

Specific examples of the conductive polymer compound of the present invention are shown below,
It is not necessarily limited to these.

The conductive metal oxide or conductive polymer compound of the present invention is used by dispersing or dissolving it in a binder.

The binder is not particularly limited as long as it has a film forming ability, for example, gelatin,
Proteins such as casein, carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, cellulose compounds such as triacetyl cellulose, dextran, agar, sodium alginate,
Sugars such as starch derivatives, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polystyrene, polyacrylamide, poly-N
-Vinylpyrrolidone, polyester, polyvinyl chloride,
Examples thereof include synthetic polymers such as polyacrylic acid.

In particular, gelatin (lime-processed gelatin, acid-processed gelatin,
Enzyme-degraded gelatin, phthalated gelatin, acetylated gelatin, etc.), acetyl cellulose, diacetyl cellulose, triacetyl cellulose, polyvinyl acetate, polyvinyl alcohol, butyl polyacrylate, polyacrylamide, dextran and the like are preferable.

In order to more effectively use the conductive metal oxide or conductive polymer compound of the present invention to reduce the resistance of the conductive layer,
It is preferable that the conductive material has a high volume content of the conductive material, but a binder of at least about 5% is necessary in order to have sufficient strength as a layer. Volume content of molecular compound is 5-95
The range of% is desirable.

The amount of the conductive metal oxide or the conductive polymer compound of the present invention used is 0.05 to 1 square meter of the photographic light-sensitive material.
20 g is preferable, and 0.1-10 g is particularly preferable. The surface resistivity of the conductive layer of the present invention is 10 ¹² Ω or less, preferably 10 ¹¹ Ω or less in an atmosphere of 25 ° C. and 25% RH. Thereby, good antistatic property can be obtained.

In the present invention, at least one conductive layer containing the conductive metal oxide or the conductive polymer compound of the present invention is provided as a constituent layer of the photographic light-sensitive material. For example, any of a surface protective layer, a back layer, an intermediate layer, an undercoat layer and the like may be used, but two or more layers may be provided if necessary.

In the present invention, a further good antistatic property can be obtained by using a fluorine-containing surfactant together with the above conductive substance.

The preferred fluorine-containing surfactant used in the present invention has a fluoroalkyl group, an alkenyl group or an aryl group having 4 or more carbon atoms, and an anionic group (sulfonic acid (salt), sulfuric acid (salt) as an ionic group. ), Carboxylic acid (salt), phosphoric acid (salt)), cation group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine group (carboxyamine salt, carboxyammonium salt, erphoamine salt, Surfactants having a sulfoammonium salt, a phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group or sorbitan residue) can be mentioned.

These fluorine-containing surfactants are disclosed in JP-A-49-10722, British Patent 1,330,356, U.S. Patents 4,335,201 and 4,347,30.
8, British Patent 1,417,915, JP-A-55-149938, 5
8-196544, British Patent 1,439,402, and the like.

Some of these specific examples are described below.

F-1 C ₈ F ₁₇ SO ₃ K The layer to which the fluorine-containing surfactant of the present invention is added is not particularly limited as long as it is at least one layer of a photographic light-sensitive material, and examples thereof include a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer and a back layer. it can. Among them, the preferred place of addition is the surface protective layer, and either the emulsion layer side or the back layer side may be used, but it is more preferable if it is added to both surface protective layers.

When the surface protective layer is composed of two or more layers, either layer may be used, or the surface protective layer may be further overcoated and used.

The amount of the fluorine-containing surfactant used in the present invention may be 0.0001 to 1 g per square meter of the photographic light-sensitive material, more preferably 0.0002 to 0.25 g, and particularly preferably 0.0003 to
It is 0.1 g.

Further, two or more kinds of the fluorine-containing surfactant of the present invention may be mixed.

Next, another antistatic agent can be used in combination with the layer containing the fluorine-containing surfactant of the present invention or another layer, and a more preferable antistatic effect can be obtained by doing so.

In the present invention, when the hydrophilic colloid layer coating liquid is applied and then dried, 300% or less of water is added based on the binder dry weight.
It is necessary to dry under the condition of relative humidity of 0% or less. When the hydrophilic colloid layer coating liquid contains more than 300% of water based on the dry weight of the binder, in the present invention, 50% is added after the point where the water content becomes 300% in the latter half of the drying.
It is necessary to dry at the following relative humidity.

When two or more hydrocolloid layers are applied and dried at the same time, the water content represents the sum of the water content of all layers, and the binder dry weight represents the sum of the binder dry weight of all layers.

The relative humidity of the present invention is the ratio of the amount of water vapor contained in a given volume to the amount of saturated water vapor in the air, expressed as a percentage.

In the present invention, the temperature for drying water of 300% or less based on the dry weight of the binder is usually preferably in the range of 25 ° C to 50 ° C.

Drying in the present invention means reducing the water content until the surface of the photosensitive material does not have tackiness, preferably 15% or less based on the dry weight of the binder,
Especially, it means to reduce the water content so that it becomes 10% or less.

The heat treatment of the present invention needs to be performed at a temperature of 30 ° C or higher, preferably 35 ° C or higher and 50 ° C or lower, more preferably 35 ° C.
It can be applied in the range of 45 ° C or lower. The heat treatment time is required to be 6 hours or more, and if it is shorter than this, the effect of the present invention is insufficient.

The heat treatment of the present invention can be applied at any time after coating and drying the silver halide photographic light-sensitive material. Generally, a silver halide photographic light-sensitive material is manufactured by a process in which after coating and drying, the material is once wound into a roll, and then cut into a predetermined size and packaged. Therefore, the heat treatment of the present invention is carried out, for example, when the silver halide photographic light-sensitive material is stored at an absolute humidity of 1% or less, when it is wound into a roll after coating and drying, when it is cut, or when it is packaged. Etc. can be applied at any time.

The humidity during the heat treatment should be 1% or less absolute humidity, and more preferably 0.8% or less. Absolute air humidity is defined as the ratio of the weight of water vapor in the air to the weight of air. For example, 1% absolute humidity is about 50% RH relative humidity at 25 ° C.
At 40 ° C, the relative humidity is about 21% RH.

In the present invention, the silver halide photographic light-sensitive material needs to be stored under the condition that the absolute humidity is 1% or less. The term "storing" as used herein means that a general user places the light-sensitive material under the conditions of the present invention until the light-sensitive material is used.

For this purpose, for example, a method is used in which the silver halide photographic light-sensitive material, which has been left in this temperature and humidity atmosphere for a sufficient time, is hermetically sealed with a moisture-proof packaging material. As another method, a method is also used in which the moisture content of the core or paper to be packaged together with the silver halide photographic light-sensitive material is reduced in advance, and the temperature and humidity inside the package after sealing the package are kept at an absolute humidity of 1% or less. be able to.

Further, a method of hermetically packaging a desiccant such as silica gel together with a silver halide photographic light-sensitive material is also effective.

The package for hermetically sealing the silver halide photographic light-sensitive material of the present invention may have any shape as long as it can seal the silver halide photographic light-sensitive material. Use of the light-sensitive material to be sealed And various shapes of the package can be considered according to the shape. Usually, a packaging bag made by heat sealing is preferably used. The material of which the packaging bag is made is a polyethylene film with a low moisture permeability (usually polyethylene containing carbon black, etc., in order to have a light-shielding property and a polyethylene surface with a slip, etc.
A material containing a substance that does not adversely affect the light-sensitive material) is preferable. Another preferable form is a packaging bag in which aluminum thin films are laminated. Preferred examples of these packaging bags include the packaging materials disclosed in JP-A-57-6754, JP-A-58-132555 and JP-A-61-189936.

When the silver halide photographic light-sensitive material of the present invention is packaged in these packaging bags, it may be packaged under reduced pressure to reduce the air in the packaging bag.

That is, in the present invention, it is necessary that the photosensitive material is placed in an atmosphere having an absolute humidity of 1% or less until the general user uses the photosensitive material.

The polyester used for the support of the present invention is a polyester mainly composed of aromatic dibasic acid and glycol, and typical dibasic acids are terephthalic acid, isophthalic acid, p-β-oxyethoxybenzoic acid. , Diphenyl sulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenylenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc., and glycol as ethylene glycol. , Propylene glycol, butanediol, neopentylene glycol, 1,4
-Cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-bisoxyethoxybenzene, bisphenol A, diethylene glycol, polyethylene glycol and the like.

Among the polyesters composed of these components, polyethylene terephthalate is most convenient from the viewpoint of easy availability.

The thickness of the polyester is not particularly limited, but is about 12μ
A thickness of about 500 μ, preferably about 40 μ to 200 μ is advantageous from the viewpoint of easy handling and versatility. In particular, a biaxially stretched crystallized product is convenient in terms of stability and strength.

The polyester support of the present invention may be optionally coated with an undercoat layer containing gelatin, a styrene-butadiene copolymer, vinylidene chloride, an aqueous polyester, an aqueous polyurethane or the like before coating the hydrocolloid layer. . In particular, an undercoat layer containing vinylidene chloride is preferably used and, in combination with the present invention, exhibits a remarkable dimensional stability improving effect. or,
In the present invention, the surface of the polyester support may be subjected to a surface treatment such as a corona treatment or a glow discharge treatment before applying these undercoat layers.

The back layer is a layer in which a hydrophilic colloid such as gelatin is used as a binder, and may be a non-photosensitive layer having a one-layer structure or a multi-layer structure having an intermediate layer, a protective layer and the like.

The back layer has a thickness of 0.1 μ to 10 μ, and if necessary, a gelatin hardening agent, a surfactant, a matting agent, colloidal silica, as well as a silver halide emulsion layer and a surface protective layer.
It may contain slip agents, UV absorbers, dyes, thickeners and the like.

In the present invention, the hydrazine derivative used for obtaining a high-contrast image is represented by the following general formula (I).

General formula (I) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarnebonyl group, G ₁ Is a carbonyl group, a sulfonyl group, a sulfoxy group, Or an iminomethylene group, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Represents a group.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, a carbonamide group or the like.

The aromatic group represented by R ₁ in the general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be bonded to a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Among these, there are isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring and the like, and among them, those containing benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and a typical substituent is a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms),
Aralkyl group (preferably 1 to 1 carbon atoms in the alkyl part)
3 monocyclic or bicyclic), alkoxy group (preferably having 1 to 20 carbon atoms), substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms), acylamino group ( Preferably, those having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms) and the like.

The alkyl group represented by R ₂ in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms and substituted with a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group or the like. It may have a group.

The aryl group represented by R ₂ is preferably a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group or the like.

The alloloxy group is preferably a monocyclic one, and the substituent includes a halogen atom and the like.

The amino group is preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms or an arylamino group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group or the like. The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group or the like.

Preferred among the groups represented by R ₂ are hydrogen atom, alkyl group (for example, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group) when G ₁ is a carbonyl group. Group), an aralkyl group (eg, an o-hydroxybenzyl group),
An aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, etc.) and the like, and a hydrogen atom is particularly preferable.

When G ₁ is a sulfonyl group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxyphenylmethyl group), an aryl group (eg, phenyl group) or a substituted amino group. A group such as a dimethylamino group is preferable.

When G ₁ is a sulfoxy group, preferred R ₂ is a cyanobenzyl group, a methylthiobenzyl group, or the like, In the case of, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly,
A phenoxy group is preferred.

When G ₁ is an N-substituted or unsubstituted iminomethylene group, preferred R ₂ is a methyl group, an ethyl group or a substituted or unsubstituted phenyl group.

As the substituent of R _2, the substituents enumerated for R ₁ can be applied, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an anikenyl group,
Alkynyl group, nitro group, etc. can also be applied.

A carbonyl group is most preferable as G in the general formula (I).

Further, R ₂ may be _one which causes a cyclization reaction in which the G ₁ -R ₂ moiety is split from the residual molecule to form a cyclic structure containing an atom of the —G—R ₂ moiety. In the general formula (a)
It can be represented by

In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, is a group capable of splitting the G ₁ -R ₃ -Z ₁ moiety from the remainder molecule, R ₃ than that removing one hydrogen electrons from R _2, Z ₁ is a nucleophilic attack to _{G 1, G 1, R 3} ,
A cyclic structure can be generated by Z ₁ .

More specifically, Z ₁ is easily converted to G ₁ when the hydrazine compound of the general formula (I) produces the next reaction intermediate due to oxidation or the like.
Is a group capable of nucleophilically reacting with R ₁ -N = N-G ₁ -R ₃ -Z ₁ R ₁ -N = N group to split from G ₁ , specifically, OH, SH, or NHR ₄ ( R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₅ , or —SO ₂ R ₅ , and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), COOH, etc. It may be a functional group which directly reacts with G ₁ (here, OH, SH, NHR ₄ , and -COOH may be temporarily protected so as to generate these groups by hydrolysis of alkali or the like. ), Or (R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G ₁ by reacting with a nucleophile such as a hydrogen ion or a sulfite ion. It may be a functional group capable of

The ring formed by G ₁ , R ₃ and Z ₁ has 5 members or 6
Preferred.

Among those represented by the general formula (a), those represented by the general formulas (b) and (c) can be mentioned as preferable ones.

General formula (b) In the formula, ▲ R ¹ _b ▼ to ▲ R ⁴ _b ▼ are a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), an alkenyl group (preferably having 1 to 12 carbon atoms), an alkenyl group (preferably Represents an aryl group (preferably having 6 to 12 carbon atoms), etc., and may be the same or different.
B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1, and
(N + m) is 1 or 2.

The 5- or 6-membered ring formed by B is, for example, a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring or a quinoline ring.

Z ₁ has the same meaning as general (a).

General formula (c) In the formula, ▲ R ¹ _c ▼ and ▲ R ^c ₂ ▼ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom or the like, and may be the same or different.

R ³ _c represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents 0 or 1 and q represents 1 to 4.

▲ R ¹ _c ▼, ▲ R ² _c ▼ and ▲ R ³ _c ▼ may combine with each other to form a ring as long as Z ₁ has a structure capable of intramolecular nucleophilic attack on G ₁ .

▲ R ¹ _b ▼ and ▲ R ² _c ▼ are preferably hydrogen atom, halogen atom or alkyl group, and ▲ R ³ _c ▼ are preferably alkyl group or aryl group.

q is preferably 1 to 3, when q is 1, p is 1 or 2, when q is 2, p is 0 or 1, and when q is 3, p is 0 or 1, and q is 2 Or when 3 ▲ CR ¹ _c R
² _c ▼ may be the same or different.

Z ₁ has the same meaning as in formula (a).

A ₁ and A ₂ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is −0.5 or more). An acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is −0.5 or more, or a linear or branched or cyclic unsubstituted or substituted fat Group acyl group (eg, a substituent includes a halogen atom, an ether group, a sulfonamide group, a carbonamido group, a hydroxyl group, a carboxy group, and a sulfonic acid group). As A ₁ and A ₂ , a hydrogen atom is most preferable.

R ₁ or R _{2 in} the general formula (I) may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties,
For example, it can be selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like.

R ₁ or R _{2 in} the general formula (I) may be one in which a group that enhances adsorption on the surface of silver halide grains is incorporated. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, triazole group and the like, U.S. Pat. Nos. 4,385,108, 4,459,347, and JP-A-59-1.
95,233, 59-200,231, 59-201,045, 59-20
1,046, 59-201,047, 59-201,048, 59-201,
049, JP 61-170,733, 61-270,744, 62-94
No. 8, Japanese Patent Application No. 62-67,508, No. 62-67,501, No. 62-67,510
The groups described in No.

Specific examples of the compound represented by formula (I) are shown below.
However, the present invention is not limited to the following compounds.

Examples of the hydrazine derivative used in the present invention include RESEARCH DISCLOSURE Item 23516 (1983, 1
January issue, P.346) and the documents cited therein, as well as U.S. Patent Nos. 4,080,207, 4,269,929, 4,276,364, and
4,278,748, 4,385,108, 4,459,347, 4,56
0,638, 4,478,928, U.S. Pat.No. 2,011,391B, JP-A-60-179734, JP-A-61-170,733, JP-A-61-270,744.
No. 62-948, EP 217,310, Japanese Patent Application No. 61-175,234,
61-251,482, 61-268,249, 61-276,283,
62-67,508, 62-67,529, 62-67,510, 62-5
8,513, 62-130,819, 62-143,469, 62-166,
Those described in No. 117 can be used.

The addition amount of the hydrazine derivative in the present invention is 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, and particularly 1 mol per mol of silver halide.
It is preferably in the range of ^10-5 to ^110-2 mol.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic gelatin hardening agent. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β
-(Vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
s-triazine etc.), mucohalogen acids (mucochloric acid etc.), N-carbamoylpyridinium salts ((1-
Morpholinocarbonyl-3-pyridinio) methanesulfonate etc.) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate etc.) can be used alone or in combination. Among them, JP-A-53-41220 and JP-A-53-5725
7, the active vinyl compounds described in 59-162546 and 60-80846 and the active halides described in US Pat. No. 3,325,287 are preferable.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The particle size distribution is basically not limited, but it is preferably monodisperse. The monodispersion as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have a regular crystal such as a cube or octahedron,
In addition, it may have irregular crystals such as spheres or plates, or may have a composite form of these crystal forms.

The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. are allowed to coexist in the process of forming silver halide grains or physically ripening. Good.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization and reduction sensitization are used. Also, noble metal sensitization methods are known, and any of these may be used alone or in combination for chemical sensitization.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, alginate sozo,
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Synthetic hydrophilic polymeric substances can be used.

As the gelatin, in addition to coal-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate may also be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halo-substituted compounds), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as Oxazoline thiones; azaindenes such as tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzene Luffin acid, can be added to many of the compounds known to the antifoggants or stabilizers, such as hydroquinones.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, a slip property improving agent, an emulsifying dispersion agent, an adhesive preventing agent and a photographic property improving agent (for example, development acceleration, high contrast). Various surfactants may be included for various purposes such as sensitization and sensitization).

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulphonates, alkyl benzene sulphonates Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene A carboxy group, such as alkyl phosphates,
Anionic surfactants containing an acidic group such as a sulfo group, a phospho group, a sulfate ester group, and a phosphate ester group; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, complex such as pyridinium and imidazolium Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. Also, a polymer latex such as a polyalkyl acrylate may be incorporated for dimensional stability.

Further, spherical particles such as polymethylmethacrylate or amorphous particles such as silicon dioxide can be contained as a matting agent for the purpose of preventing adhesion between sensitive materials, improving writing properties, and improving vacuum sealability. Average particle size is 0.1μ
-10 μm, preferably 1-5 μm.

Suitable development accelerators or accelerators for nucleating infectious development used in the present invention include JP-A Nos. 53-77616 and 54-37732.
In addition to the compounds disclosed in Nos. 53-137133, 60-140340 and 60-14959, various compounds containing N or S atoms are useful.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or U.S. Pat.
It is not necessary to use the highly alkaline developing solution described in No. 5 having a pH close to 13, and a stable developing solution can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ion as a preservative in an amount of 0.15 mol / l or more and has a pH of 10.5-1.
With a developer having a pH of 2.3, particularly pH 11.0 to 12.0, a sufficiently high negative tone image can be obtained.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-).
3-pyrazolidone), aminophenols (eg N-
(Methyl-p-aminophenol) and the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention is particularly processed with a developer containing dihydroxybenzenes as a main developing agent, dihydroxybenzenes as an auxiliary developing agent, and 3-virazolidones or aminophenols as an auxiliary developing agent. Suitable for In this development, dihydroxybenzenes are preferably used in an amount of 0.05 to 0.5 mol / l and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol / l or less.

Also, as described in U.S. Pat.No. 4,269,929,
By adding amines to the developing solution, the developing speed can be increased and the developing time can be shortened.

Other developers include alkyl metal sulfites, carbonates,
A development inhibitor such as a pH buffer such as borate and phosphate, bromide, iodide, and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant You can Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), a defoaming agent, a hardener, and a silver stain preventing agent for the film. (For example, 2-mercaptobenzimidazole sulfonic acids, etc.) may be included.

On the other hand, the fixing solution is an aqueous solution containing thiosulfate, a water-soluble aluminum compound, acetic acid and a dibasic acid (for example, tartaric acid, citric acid or salts thereof), and has a pH of 4.4 or higher, preferably 4.6 to 5.4, more preferably Has 4.6-5.0.

The pH of the fixer changes the swelling of the film and significantly affects the residual color. That is, if the pH exceeds 5.4, the swelling of the film is large even if a predetermined hardener is introduced, and transport problems such as poor drying and poor passage occur, and if a large amount of hardener is introduced to prevent it, the Film contamination occurs due to deposition of film agent. On the other hand, a pH of 4.4 or less causes residual color, and a pH of 4.0 or less causes problems such as fixing failure. However, with the above pH range and the amount of the hardener of the present invention, it becomes possible to quickly obtain a film with less residual color.

The fixing agent contains thiosulfates such as sodium thiosulfate and ammonium thiosulfate as an essential component, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 5 mol / l.

Examples of the acidic hardening agent in the fixing solution in the present invention include water-soluble aluminum salts, chromium salts, and ethylenediaminetetraacetic acid complex using a trivalent iron compound as an oxidizing agent. Preferred compounds are water-soluble aluminum salts such as aluminum chloride, aluminum sulfate and potassium alum.
The preferred addition amount is 0.01 mol to 0.2 mol / l, and more preferably 0.03 to 0.08 mol / l.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. These compounds are the fixer 1
It is effective to contain more than 0.005 mol per
1 to 0.03 mol / l is particularly effective.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, sodium potassium tartrate, ammonium tartrate, ammonium potassium tartrate, potassium aluminum tartrate, antimony potassium tartrate, antimony sodium tartrate, lithium hydrogen tartrate, Examples include lithium tartrate, magnesium hydrogen tartrate, potassium boron tartrate, and lithium potassium tartrate.

Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

The fixer may optionally contain preservatives (eg sulfite, bisulfite), pH buffers (eg acetic acid, boric acid), pH adjusters (eg sulfuric acid), chelating agents (described above). . The pH buffer here is 10-40% because the pH of the developer is high.
g / l, more preferably about 18-25 g / l is used.

The fixing temperature and time are the same as in the case of development.
10 seconds to 1 minute at about 50 ° C is preferred.

According to the method of the present invention, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and preferably from about 20 ° C to about 50 ° C for 10 seconds to 3 minutes. Drying is performed at about 40 ° C to about 100 ° C, and the drying time can be appropriately changed depending on the ambient conditions.
Generally, it may be about 5 seconds to 3 minutes and 30 seconds.

U.S. Pat. No. 3025 for a roller transport type automatic processor
No. 779, No. 3545971, etc., and is referred to simply as a roller transport type processor in the present specification. The roller-conveying processor comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. .

The development processing temperature and fixing processing temperature are selected between about 18 ° C and 50 ° C, more preferably 25 ° C to 43 ° C.

The developing method of the present invention is particularly suitable for rapid processing using an automatic processor. As the automatic developing machine, either a roller-conveying machine or a belt-conveying machine can be used. The processing time can be short, total 2 minutes or less, especially 100 seconds or less,
Among them, the time allotted for development is 15 seconds to 60 seconds, the fixing time is 10 seconds to 40 seconds, and the washing time is 10 seconds to 60 seconds, which is sufficiently effective for rapid processing.

In the developer of the present invention, a silver stain preventing agent is disclosed in JP-A-56-24347.
The compounds described in No. 1 can be used. The compounds described in JP-A-61-267759 can be used as a dissolution aid added to the developer. Further, as the pH buffer used in the developing solution, the compounds described in JP-A-60-93433 or the compounds described in JP-A-62-186256 can be used.

(Effects of the Invention) According to the present invention, a silver halide photographic light-sensitive material having a superhigh contrast, few pinholes, and excellent dimensional stability associated with development processing is obtained by using a stable developing solution. be able to.

The present invention will be described in detail below with reference to examples.

In the examples, the developer and fixer having the following formulations were used.

Developer Hydroquinone 50.0g N-Methyl-p-aminophenol 0.3g Sodium hydroxide 18.0g 5-Sulfosalicylic acid 55.0g Potassium sulfite 110.0g Ethylenediaminetetraacetic acid disodium 1.0g Potassium bromide 10.0g 5-Methylbenzotriazole 0.4g 2 -Mercaptobenzimidazole-5-sulfonic acid 0.
3g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2g N-n-butyldiethanolamine 15.0g Sodium trienesulfonate 8.0g Add water 1 Adjust to pH = 11.6 (add potassium hydroxide) pH 11.6 Hardening agent Ammonium thiosulfate 180g Sodium thiosulfate pentahydrate 45g Sodium sulfite 18g Ethylenediaminetetraacetic acid 0.4g Tartaric acid 4.0g Glacial acetic acid 30.0g Aluminum sulphate 11.0g Water is added to bring pH to 4.7.

Example 1 Biaxially stretched 100 μm thick polyethylene terephthalate support on both sides with zeratan 14 mg / m ² , a subbing layer on both sides so that the reaction product of polyamide epichlorohydrin consisting of diethylenetriamine and adipic acid 9 mg / m ^2. Applied. Next, a conductive layer having the following formulation- (1) and a gelatin layer having the following formulation- (2) were coated on one surface. Further, a back layer and a protective layer of the following prescription- (7) and (8) are sequentially applied thereon, and the following prescription- (3), (4), (5), on the opposite surface.
The silver halide emulsion layer and the protective layer of (6) are sequentially coated,
A sample was prepared by drying under the conditions shown in Table-1.

Formulation (1) Conductive layer SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 165 mg / m ² gelatin 19 mg / m ² Formulation (2) Gelatin layer gelatin 35 mg / m ² Salicylic acid 17 mg / m ² Diethylenetriamine Reaction product of polyamide composed of adipic acid and epichlorohydrin 6 mg / m ² Formulation (3) Silver halide emulsion layer-1 I liquid; 300 ml of water, gelatin 9 g II liquid; AgNO ₃ 100 g, 400 ml of water III liquid; NaCl 37 g, (NH ₄ ) ₃ RhCl 1.1 ml, water 400 ml Solution II and solution III were simultaneously added to solution I kept at 45 ° C at a constant rate. After removing the soluble salts from this emulsion by a conventional method well known to those skilled in the art, gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer. The average grain size of this emulsion is 0.20μ
The amount of gelatin contained per 1 kg of emulsion was 60 g.

The following compounds were added to the emulsion thus obtained.

Compound Example I-30 of the Invention I-30 5 × 10 ⁻³ mol / Ag 1 mol Compound-1 60 mg / m ² Compound-2 9 mg / m ² Polystyrenesulfonic acid sodium salt 40 mg / m ² N-oleoyl-N-methyltaurine sodium 50 mg salt
/ m ² 1,2-bis (vinylsulfonylacetamide) ethane 70m
g / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 0.46
g / m ² The coating amount thus obtained was coated so that the coated silver amount was 2 g / m ² .

Compound-1 Compound-2 Formulation- (4) Silver Halide Emulsion Layer-2 Solution I; Water 300 ml, Gelatin 9 g Solution II; AgNO ₃ 100 g, Water 400 ml III Solution; NaCl 37 g, (NH ₃ ) RhCl ₆ 2.2 mg 400 ml Formulation- (3) Emulsion Liquid II and III in liquid I in the same manner as
The liquid was added at the same time to prepare an emulsion. This emulsion was a monodisperse emulsion having an average grain size of 0.20μ.

The following compounds were added to the emulsion thus obtained.

Compound I-30 of the present invention 5 × 10 ⁻³ mol / Ag 1 mol Compound-1 60 mg / m ² 〃 −29 mg / m ² Polystyrenesulfonic acid sodium salt 50 mg / m ² N-oleoyl-N-methyltaurine sodium salt 40 mg
/ m ² 1,2-bis (vinylsulfonylacetamide) ethane 80m
g / m ² 1-Phenyl-5-mercaptotetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.05 μ) 40 mg
/ m ² The coating liquid thus obtained was coated so that the coating silver amount was 2 g / m ² .

Prescription - (5) protective layer -1 Gelatin 1.0 g / m ² lipoic acid 5 mg / m ² sodium dodecylbenzenesulfonate 5 mg / m ² Compound -3 20 mg / m ² of polystyrene sulphonic acid sodium salt 10 mg / m ² Compound -4 20mg / m ² Ethyl acrylate latex (average particle size 0.05μ) 200m
g / m ² prescription- (6) Protective layer-2 Gelatin 1.0 g / m ² Polymethylmethacrylate fine particles (average particle size 2.5
μ) 60 mg / m ² dodecylbenzene sulfonic acid sodium salt 20 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potassium salt 3 mg / m ² polystyrene sulfonic acid sodium salt 2 mg / m ² poly (degree of polymerization 5) oxy Sulfonate sodium salt of ethylene nonyl phenyl ether 20mg / m ² Compound-3 Compound-4 Prescription- (7) Back layer Gelatin 2.5g / m ² compound-5 Compound-6 Compound-7 Dodecylbenzenesulfonic acid sodium salt 50 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 20 mg / m ² Polystyrenesulfonic acid sodium salt 40 mg / m ² 1,3-Divinylsulfonyl-2-propanol 150 mg / m ² Ethyl acrylate latex (Average particle size 0.05μ) 500m
g / m ² prescription- (8) Protective layer-3 Gelatin 1g / m ² Polymethylmethacrylate fine particles (average particle size 3.4μ) 40m
g / m ² Dodecylbenzenesulfonic acid sodium salt 15 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 10 mg
/ m ² Polystyrenesulfonic acid sodium salt 20 mg / m ² Sodium acetate 40 mg / m ^{2 The} obtained sample was cut into a size of 25 cm × 30 cm, and heat-treated under the conditions shown in Table 1. After that, it was left in an atmosphere of 25 ° C. and 40% RH (absolute humidity: about 0.79%) for 6 hours and then hermetically sealed in a moisture-proof bag. As a moisture-proof bag, the embodiment of JP-A-61-189936-
The invention product (8) described in 1 was used.

After leaving the sample sealed in a moisture-proof bag for 2 weeks in an atmosphere of 25 ° C, use the following methods to measure the surface resistivity of the conductive layer, the state of pinholes, dimensional changes due to development processing, and absolute inside of the moisture-proof bag. Humidity was measured. The results are shown in Table-1.

As is clear from Table-1, Samples 1, 2, 5 to 7 of the present invention have significantly less pinholes, and the dimensional change accompanying development processing is small.

1. Surface resistivity After leaving the sample for 12 hours at 25 ℃ and 25% RH, the electrode interval is 0.14cm, length
It was sandwiched between 10 cm brass electrodes (the part in contact with the sample is made of stainless steel), and the value after 1 minute was measured using an electrometer TR8651 manufactured by Takeda Riken.

2. Pinhole The resulting sample was rubbed with a neoprene rubber roller at 25 ° C and 25% RH in a normal room where air cleaning was not performed, and then exposed and developed (38 ° C 20 ″) to generate a pinhole. The situation was evaluated.

3. Evaluation method of dimensional change due to development processing Two holes with a diameter of 8 mm were opened in the sample at intervals of 200 mm, and 25
After leaving it in a room at 30% RH for 2 hours, the distance between the two holes was accurately measured using a pin gauge with a precision of 1/1000 mm. The length at this time is Xmm. Then, after developing, fixing, washing with water and drying with an automatic processor, the dimension after 5 minutes is Ymm.
And Dimensional change rate (%) The value was evaluated.

In the industry, if the dimensional change rate is ± 0.01% or less, there is no problem in practical use.

FG-660F automatic developing machine manufactured by Fuji Photo Film Co., Ltd. was used for the development process, and GR-D1 and GR-F1 manufactured by the same company were used for the developer and fixer.
The treatment was performed at 38 ° C for 20 seconds. The drying temperature at that time was 45 ° C.

4. Measurement of absolute humidity inside the moisture-proof bag The relative humidity inside the bag was measured under a temperature condition of 25 ° C, and the absolute humidity was calculated using a psychrometric chart.

The relative humidity was measured using a thermo-hygrometer MODEL HN-U ₂ HUMI-TEMP RECORDER (Chino Co., Ltd.) (sensor HN-L20 (Chino Co., Ltd.)). Was converted to absolute humidity using a psychrometric chart.

Example-2 In the sample-1 of Example-1, a sample in which the ratio of the conductive metal oxide and gelatin in the conductive layer was changed as shown in Table-2 and a sample in which the conductive layer was changed to a conductive polymer compound were prepared. Created. For this sample, in the same manner as in Example-1, a pinhole,
The dimensional change was evaluated. The results are shown in Table-2.

As is apparent from Table-2, in Samples 9 to 15 of the present invention, generation of pinholes was extremely small, and it was found that the dimensional change accompanying development processing was small.

Example-3 Both sides of the same support as in Example-1 were subjected to corona discharge treatment under the following conditions, and then an aqueous dispersion of a copolymer of methyl methacrylate / butyl acrylate / acrylonitrile = 45/45/10 wt% was obtained as a solid content. Was applied and dried so as to be 0.3 g / m ² . After the corona discharge treatment, an aqueous dispersion of a copolymer of vinylidene chloride / methyl methacrylate / acrylonitrile = 90/8/2% by weight was applied on both surfaces so that the solid content was 1 g / m ² , and dried. Furthermore, corona discharge treatment after gelatin 0.1 g / m ^2, compound -13,5mg / m ^2, was coated on both sides so as to become methylcellulose (Shin-Etsu Chemical Co., Ltd. 60SH-6) 5mg / m ² dry thereon did.

Corona discharge treatment conditions: A solid state corona treatment machine manufactured by Pillar Co., 6 kVA model is used to treat a 30 cm wide support at 20 m / min. At this time, the object to be processed is 0.375 kVA according to the current and voltage readings.
/ min / m ² was processed. The discharge frequency during processing is 9.6KH
z, gap clearance between electrode and dielectric roll h1.6mm
Met.

One side, a conductive layer, a gelatin layer, a back layer and a protective layer were sequentially coated on the support thus obtained in the same manner as in Sample-1 of Example-1, and on the other side a silver halide emulsion layer and A protective layer was sequentially applied to prepare Sample-17. After 2 weeks at 25 ° C., this sample was used to evaluate pinholes, dimensional changes and the like in the same manner as in Example-1.

The results are shown in Table-3.

As is clear from Table 3, Sample-17 having a vinylidene chloride copolymer layer having a low water vapor transmission rate is better than Sample-1 of the present invention in dimensional change due to development processing, and pinholes are more remarkable. You can see that there are few.

Example 4 Biaxially stretched 100 μm thick polyethylene terephthalate support with gelatin 14 mg / m ^{2 on} both sides, a reaction product of polyamide epichlorohydrin consisting of diethylenetriamine and adipic acid 9 mg / m ² was applied on both sides, The surface was coated with the conductive layer of the formulation- (1) of Example-1 and the gelatin layer of the formulation- (2). Next, the following prescription- (9),
The back layer and the protective layer of (10) were sequentially applied.

Formulation-9 Gelatin 3 g / m ² compound-8 40 mg / m ² compound-5 120 mg / m ² compound-6 40 mg / m ² compound-7 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 40 mg
/ m ² Dodecylbenzenesulfonic acid sodium salt 40 mg / m ² 1,3-divinylsulfonyl-2-propanol 120 mg / m ² prescription-10 gelatin 0.8 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 30 m
g / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m
² Dodecylbenzenesulfonic acid sodium salt 15 mg / m ² Sodium acetate 40 mg / m ² Compound-8 Then, on the opposite surface, 4 × 10 ^-7 mol of iridium per 1 mol of Ag was added, the silver iodide content was 0.5 mol%, and the silver bromide content was 9 mol.
A 9.5 mol% silver halide emulsion (unchemically sensitized emulsion) was prepared by a conventional method well known in the art, and after removing soluble salts, gelatin was added. The average grain size of this emulsion is
A 0.28 µ monodisperse emulsion had 99 g of Ag and 56 g of gelatin per kg of the emulsion.

In this emulsion, as a sensitizing dye, 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine sodium salt 11 mg / m ² , 3- (3-sulfopropyl) -3 '-(4-sulfobutyl) -5'-phenyl-4,5-dibenzoxocyanine sodium salt 6.9
mg / m ² , 6-methyl-4-hydroxy-1, as a stabilizer,
3,3a, 7-Tetrazaindene 8 mg / m ² , Compound Examples I-5 and I-19 were used as the hydrazine derivative at 1.2 × 10 ⁻³ respectively.
Mol / Ag 1 mol, 5 × 10 ⁻⁵ mol / Ag 1 mol, compound-9 5 mg / m ² as a nucleation accelerator was added, and further ethyl acrylate latex (average particle size 0.05 μ) 600 mg / m ² , compound-10 polymer latex 195 mg / m 1,2-bis (vinylsulfonyl acetamide) as a ² hardener ethane 140 mg / m ^2, 2,
4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 12 mg / m ² , N-oleoyl-N-methyltaurine sodium salt 40 mg / m ² as a surfactant, polyethylene sulfonic acid as a thickener Sodium salt 20 mg / m ² was added.

The emulsion prepared as described above was coated so that the coated silver amount was 3.5 g / m ² , and the following formulation was used as a protective layer.
(11) and (12) were sequentially applied. The drying conditions during coating are shown in Table-4.

Formulation-11 Gelatin 1.0g / m ² L-ascorbic acid 30mg / m ² Hydroquinone 190mg / m ² Ethyl acrylate latex (average particle size 0.05μ) 240m
g / m ² Polystyrene sulfonic acid sodium salt 3 mg / m ² prescription-12 gelatin 0.6 g / m ² Polymethylmethacrylate fine particles (average particle size 2.5 μ) 60 m
g / m ² Liquid organopolysiloxane (gelatin dispersion) 10 mg / m
² Dodecylbenzenesulfonic acid sodium salt 20 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potassium salt 4 mg / m ² Colloidal silica 90 mg / m ² Compound-9 Compound-10 The obtained sample was heat-treated under the conditions shown in Table 4 and sealed and packaged in the same manner as in Example-1. After standing at 25 ° C. for 2 weeks, this sample was used to evaluate pinholes and dimensional changes in the same manner as in Example-1. The results are shown in Table-4.

As is apparent from Table 4, Samples 19 to 22 of the present invention have significantly less pinholes and a smaller dimensional change due to development processing.

Continuation of the front page (56) Reference JP-A-55-52052 (JP, A) JP-A-58-147737 (JP, A) JP-A-62-280835 (JP, A) JP-A-62-231252 (JP , A) JP 63-26654 (JP, A) JP 1-229244 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the constituent layers of the silver halide photographic light-sensitive material has a surface resistivity of 25. 10 ¹² Ω or less in an atmosphere of 25 ° C RH,
Further, when the silver halide emulsion layer and other hydrophilic colloid layer coating liquid are applied on the support and then dried, based on the dry weight of the binder contained in all the layers formed on the support.
The moisture of 300% or less is dried at a relative humidity of 50% or less, and after drying, the silver halide photographic light-sensitive material is subjected to an absolute humidity of 1%.
% Heat treatment at a temperature of 30 ° C. or more for 6 hours or more, and the silver halide photographic light-sensitive material is stored in an atmosphere of absolute humidity 1% or less. material.