JPH0414039A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and dryability of the photosensitive material by reducing a coating amount of hydrophilic colloid and a swelling rate of it. CONSTITUTION:This photosensitive material is formed by laminating successively on a support a hydrophilic colloidal layer containing a solid disperse dye and a silver halide emulsion layer. The coating amount of the total hydrophilic colloids is regulated to <=2.5 g/m<2> on one side to the support, and all the hydrophilic colloidal layer are sufficiently hardened in order to suppress the swelling rate of these layers. As said dye, the compound of the shown formula and the like can be used, and as the hardener, 1,2-bis(sulfonylacetamide)ethane and the like can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photosensitive material, and particularly to a silver halide photosensitive material that can be rapidly processed and has a dye layer. The present invention also relates to a developing method thereof.

(Prior art) In recent years, commonly used black-and-white photosensitive materials (for X-ray, plate making, and microphotography) have been developed in automatic processors in a time of 1 to 5 minutes, but the number of images taken has decreased. In order to cope with the increase in the number of images, it is desired to complete the development process as quickly as possible. In addition, materials such as medical X-ray photosensitive materials, which are used to take images during surgery and feed back the results to the surgery, must be processed in the shortest possible time. The development processing time has changed from the above-mentioned 1 minute or more to less than 1 minute, and is now shifting to shorter processing times.

Higher image quality of photographic light-sensitive materials is required for medical X-ray light-sensitive materials in order to improve diagnostic accuracy. Due to the nature of photosensitive materials for plate making, which go through the turning process many times, if the photosensitive material does not have sufficient resolution, the image becomes blurred each time it goes through the turning process, which is a problem. For this reason, higher image quality is desired. In recent years, photosensitive materials for plate making have been increasingly exposed to laser light, and photosensitive materials are required to maintain high image quality even under high illuminance. Microphotosensitive materials are required to have high image quality because photographic images are viewed not directly but enlarged, and because they need to have legal evidence.

As seen above, it can be seen that rapid processing in less than 45 seconds and high image quality are required for black and white photosensitive materials.

In order to improve the image quality of photographic light-sensitive materials, photographic emulsion layers or other layers are colored to absorb light of specific wavelengths. When incident light passes through a photographic emulsion layer, or after passing, the scattered light is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material on the opposite side of the emulsion layer, and enters the photographic emulsion layer again. In order to prevent image blurring, that is, halation, caused by this, a colored layer is provided between the photographic emulsion layer and the support, or on the opposite side of the support from the photographic emulsion layer.

Such a colored layer is called an antihalation layer (AH layer). Furthermore, in X-ray photosensitive materials, a colored layer may be provided as a loss-over cut layer to reduce crossover light and improve sharpness.

These layers to be colored often consist of hydrophilic colloids and therefore dyes are usually included in the layers for their coloring. This dye must satisfy the following conditions.

(1) A material with appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. In other words, it should not adversely affect the performance of the silver halide photographic light-sensitive layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or capri.

(3) It should not be bleached or dissolved and removed during the development process, leaving no harmful residual color on the photographic material after processing.

As a method of providing a dye layer, there is a method of dissolving a dissolved dye in a hydrophilic colloid layer, as described in British Patent No. 1.414,4.
No. 56, No. 1,477.638 and No. 1,477.6
It is disclosed in No. 39.

The disadvantage of this method is that if you try to improve the residual color by increasing the water solubility of the dye, the fixation of the dye will decrease, and the dye will diffuse into the adjacent layer, causing desensitization and transfer of the dye to other light-sensitive materials. That's true. In addition, a method in which a hydrophilic polymer with an opposite charge to the dissociated anionic dye coexists in the layer as a mordant and the dye is localized in a specific layer by interaction between the dye molecules and the polymer is disclosed in US Pat. No. 548,564,
It is disclosed in 4.124,386, 3,625.694, etc. However, in this method, the presence of anionic substances other than dyes in the same layer causes unfavorable effects on manufacturing suitability, such as failure to localize the dye or aggregation of the coating solution.

As a method to improve these problems, a method in which a dye dispersed in a microcrystalline state is present between the support and the emulsion layer is disclosed in U.S. Pat. No. 4,803,150 and WO3B104794.
It is disclosed in the issue.

This method is an excellent technique for achieving high image quality without desensitization.

(Problems to be Solved by the Invention) However, this technique mainly has a problem in its suitability for rapid processing in less than 45 seconds, which has been required in recent years, and this will be discussed below.

If a new layer is provided as the AH layer, the total amount of hydrophilic colloid will be increased since the AH layer is usually formed of hydrophilic colloid. When the amount of hydrophilic colloid increases, more water is absorbed into the photosensitive material during the processing process, resulting in poor drying properties. This is a fatal problem for rapid processing of less than 45 seconds. Further, since medical X-ray photosensitive materials and microphotosensitive materials are stored for a long period of time, it is necessary that residual hypo (sodium thiosulfate) in the photosensitive materials after development is small. At this time, if the amount of hydrophilic colloid is large, the amount of hypo absorbed in the fixing solution will also increase, and in order to wash away this, the water washing time must be increased, which also poses a problem in terms of suitability for rapid processing.

In order to make silver halide photographic materials suitable for rapid processing, it is necessary to reduce the amount of hydrophilic colloid applied or add a sufficient amount of hardening agent to reduce the swelling rate during development processing. It is being done. However, if the swelling ratio of the latter is reduced, the residual color after processing tends to increase, and there is a problem in adding AHIIW to improve sharpness.

(Objective of the Invention) The object of the present invention is to provide a silver halide negative light material which has good residual color property, the above-mentioned high image quality, and can be rapidly processed, and to disclose a developing processing method for the light-sensitive material. It is.

(Means for Solving the Problems) In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a solid dispersed dye and at least one silver halide emulsion layer on a support, all hydrophilic colloids of the light-sensitive material are provided. The coating weight of the photographic element is 2.5 g/rri or less per side, and the total hydrophilic colloid layer has a swelling rate of 200 percent (where the swelling percentage is (a) After incubation treatment at cent relative humidity for 3 days, the thickness of the layer was measured.
C) immersing the photographic element in distilled water at 21°C for 3 minutes;
and (d) hardened in an amount sufficient to reduce the thickness of the layer (determined by measuring the percentage change in layer thickness compared to the layer thickness measured in step (b)). The above object has been achieved by the silver halide photographic material.

The above object was achieved by preferably developing the photosensitive material for 45 seconds or less (more preferably 30 seconds or less).

The dye used in the present invention is covered by International Patent WO3810479.
Tables 1 to X of No. 4, (I) to (■) shown below, and others are used.

- Numerical formula (1) General formula (n) General formula (II[) A = L 1 (L r = L 3 ). -to' General formula (L"ll') A=(L, -L,),,=B General formula (V) General formula (VT) General formula (■) A=C-(CH=CH÷1Q ( In the formula, A and A' may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, and X and Y may be the same or different and each represents an electron-withdrawing group. R
represents a hydrogen atom or an alkyl group, R1 and R7 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R1 and R2 may be linked to form a 5- or 6-membered ring.

R5 and Ro each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R4 and R5 each represent a hydrogen atom, or R1 and R4 or R2 and R9 are linked to form a 5- or 6-membered ring. Represents a group of nonmetallic atoms necessary to form a metal. L, , L, and each represent a methine group.

m represents 0 or l, n and q each represent 0, l or 2, p represents 0 or 1, and when p is 0, R1 represents a hydroxy group or a carboxyl group, and R4 and R6 represent hydrogen represents an atom. B' represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group.

Q represents a heterocyclic group.

However, the compound represented by the general formula (I) or ■) is
Each molecule contains at least one dissociable group having a pKa in the range of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1:I. ) First, general formula (I) or ■
) will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, inoxazolidinone, barbylic acid, thiobarbital acid, indandione, pyrazolo Represents pyridine or hydroxypyridone.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole.

Examples of heterocycles of B' include pyrrole, indole,
Thiophene, furan, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine,
phenoxazine, indoline, thiazole, pyridine,
These include pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolopyridazine, and tetrazole.

The heterocycle represented by Q is preferably a 5-membered heterocycle which may be benzo-fused, more preferably a 5-membered nitrogen-containing heterocycle which may be benzo-fused. Q
Examples of heterocycles include pyrrole, indole, pyrazole, pyrazolopyrimidone, benzindole, and the like.

A group having a dissociable proton with a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1:1 makes the dye molecule substantially water-insoluble at pH 6 or below. There is no particular restriction on the type and substitution position on the dye molecule as long as it makes the dye molecule substantially water-soluble at pH 8 or above, but preferably a carboxyl group, a sulfamoyl group, a sulfonamide group, A hydroxy group is preferred, and a carboxyl group is more preferred. The dissociative group may not be directly substituted on the dye molecule, but may be substituted via a divalent linking group (eg, alkylene group, phenylene group). Examples via a divalent linking group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxyphenyl, 2, 5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phnynylsulfamoylphenyl, 2-carboxyphenyl, 2゜4.6-doryhydroxyphenyl, 3-benzenesulfonamidophenyl, 4-(p- Cyamibensene sulfonamido) phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-4-
Carboxyphenyl, 3-methoxy-4-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-sulfamoylphenyl, 2, Examples include 5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3-galboxypropyl, 4-carboxybutyl, 8-carboxyoctyl, and the like.

The alkyl group represented by R, Rs or R6 has 1 to 1 carbon atoms.
10 alkyl groups are preferred, and examples include groups such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R and R2 is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n-
butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferred, and substituents [e.g. ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, i-propoxycarbonyl), aryloxy groups (e.g. phenoxy), phenyl groups, amide groups (e.g. acetylamino, methanesulfonamide), carbamoyl groups (e.g. methyl carbamoyl,
ethylcarbamoyl), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R1 or R2 is preferably a phenyl group or a naphthyl group, and the substituents include the above R
The substituents of the alkyl group represented by 3 and R2 include the groups and alkyl groups (eg, methyl, ethyl). ].

The acyl group represented by R or R2 is preferably an acyl group having 2 to 10 carbon atoms, and includes, for example, acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl, benzoyl, and the like. R1 or R
Examples of the alkylsulfonyl group or arylsulfonyl group represented by 2 include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, pencenesulfonyl, p-toluenesulfonyl, 0
- Groups such as hydroxybenzenesulfonyl and the like can be mentioned.

The alkoxy group represented by R1 or R4 has 1 to 1 carbon atoms.
O is preferably an alkoxy group, such as methoxy, nidoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, isopropoxy and the like. Examples of the halogen atom represented by R8 or R6 include chlorine, bromine, and fluorine.

Examples of the ring formed by connecting R1 and R4 or R2 and R3 include a julolidine ring.

Examples of the 5- or 6-membered ring formed by linking R1 and R2 include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L, , R2 or R3 may have a substituent (eg methyl, ethyl, cyano, phenyl, chlorine atom, hydroquinepropyl).

The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyan group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-lyloroheptyl), arylcarbonyl group (optionally substituted carbonyl group, such as benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl)
, alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyl Oxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-
Methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)ethoxyfethoxycarbonyl), aryloxycarbonyl group (optionally substituted aryloxy A carbonyl group, for example, phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ditylphenoxycarbonyl, 4
-Fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2
, 4-c(t-amyl)phenoxycarbonyl), a carbamoyl group (a carbamoyl group that may be substituted,
For example, carbamoyl groups ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxydiphenylcarbamoyl, 2,4-di(t-amyl)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbamoyl)phenylcarbamoyl, 3-(hexyloxycarbonyl)phenylcarbamoyl ), a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), a sulfamoyl group (a sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl).

Next, specific examples of dyes used in the present invention will be given.

I-9 ■-10 ■-11 ■-16 ■-17 ■-18 ■-19 ■-12 ■-13 ■-14 ■-15 ■-21 ■ ■-25 ■-26 ■-27 Ut knee 28 OOH ■-34 OOH ■-30 ■-37 l-3 CH8 ■ I[-6 ll-1 1[[-6 ■ ■ I[[-5 111 Shil'13 ■-10 NH3O, CH3 ■ ■ Shii3 I'+3 ■-13 ■-14 ■-15 ■-20 ■ ■-22 ■-23 OOH 0OH I[[-16 II[-17 ■-18 ■ ■-24 ■ ■-26 Is it Shith OOH ■-27 ■-28 OOH ■-29 ■-33 ■-35 OOH OOH ■-31 COCH.

C0CH.

'-COOH ■-32 OOH OOH ■-36 C,H.

V-3 C2H6 rHs OOH IV-5 IV-7 Js IV-1 OOH ■-13 Cρ IV-1 C, Hf ■-1 2H5 V-4 OOH N ■ OOH I-2 N CzH4C[JtJtl OOH CH2COOH ■-3 ■-4 COOI ( COOI COOI COOI ■-12 C COOI ■-1 COOI ■-5 COOI The dye used in the present invention is covered by International Patent W○8810479
No. 4, European Patent EPO 274723A1, No. 2
76. No. 566, No. 299,435, Japanese Unexamined Patent Publication No. 1973-
No. 92716, No. 55-155350, No. 55-15
No. 5351, No. 61205934, No. 48-6862
No. 3, U.S. Pat. No. 2,527,583, U.S. Pat. No. 3,486,897
No. 3746539, No. 3933798, No. 41
No. 30429, No. 4040841, Patent Application No. 15087
No. 4, No. 1-103751, No. 1-307363, etc., and can be easily synthesized according to the method.

The present invention is not limited to the dyes shown above.

In the present invention, the solid disperse dye refers to a solid disperse dye that cannot exist in a molecular state in the intended colored layer due to insufficient solubility of the dye itself, and as a solid of a size that is virtually impossible to diffuse in the layer. means the state of existence.

For details on the adjustment method, see International Application Publication (WO) 881047.
94, Koroppa Patent (EP) 0276566A1, JP-A No. 63-197943, etc., the method involves ball milling and stabilization with a surfactant and gelatin, and after dissolving the dye in an alkali IJ solution. , a method of lowering the pH and causing precipitation is preferably used. However, the present invention is not limited to these adjustment methods.

When a dye is contained in the undercoat layer as in the present invention, the amount of gelatin applied in the undercoat is preferably 0.5 g/n, so the size of particles that can be incorporated into the layer is limited. If large particles of 3 μm or more are contained, problems such as dye particles falling off from the dye layer will occur.However, the particle size is preferably less than 3 μm, and 1 μm or more
The thickness is preferably 0.5 μm or less, more preferably 0.5 μm or less.

Filtration, centrifugation, etc. are used as a method for removing large particles, but the present invention is not limited thereto.

The amount of dye to be used is preferably 5 .mu./i to 400 .mu./n, particularly 10 .mu./i to 250 a/n.

Further, the amount of gelatin used in the above adjustment can be any amount necessary to keep it below the amount of gelatin used in the present invention, that is, Ig/m2.

The gelatin coating layer of the colored layer in the above adjustment of the present invention is Ig/m
2 or less, preferably 0.7 g/m or less, and more preferably 2 g/m2 to 0.5 g/m2.

If the amount of total hydrophilic colloid is large, the amount of water contained in the film in the treatment solution will increase, which will worsen the drying performance, which is undesirable. Therefore, the amount of total hydrophilic colloid applied should be 2.5 per side.
g/m2 or less, preferably 2 g/nf or less.

In photographic materials, hydrophilic colloids can be used in emulsion layers, surface protection layers, subbing layers, and back layers, and the total amount of hydrophilic colloids in the present invention refers to the sum of all coated hydrophilic colloids.

, a hydrophilic colloid layer refers to a layer containing hydrophilic colloid, and a total hydrophilic colloid layer refers to the sum of those layers.

In addition, if the swelling rate of the hydrophilic colloid layer is large, a large amount of water will be absorbed into the membrane in the processing solution, which will result in poor drying properties, which is not desirable. Therefore, the swelling rate of the hydrophilic colloid layer will be 200% (here The percentage is determined by (a) incubating the photographic element at 38° C. 150 percent relative temperature for 3 days, (b1 layer thickness being measured, and (C)
The photographic element was immersed in distilled water at 21° C. for 3 minutes and (
d) determined by measuring the percentage change in layer thickness compared to the layer thickness measured in step (b)) is preferably below 170%, more preferably below 170%. However, if the swelling is too small, it becomes difficult for the processing liquid to permeate into the film, resulting in poor development performance, fixing speed, etc., which is a problem.

Therefore, the swelling ratio needs to be at least 120%.

Gelatin is a typical hydrophilic colloid, but any other conventionally known colloid used for photography can be used.

The silver halide emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase.
For example, the emulsion may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a prefogged direct reversal type emulsion). Preferably,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
It is a tabular grain emulsion in which grains having a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area. A monodispersed emulsion having the above coefficient of variation (value S/d, which is the standard deviation S divided by the diameter d in a distribution expressed by a diameter when the projected area is approximated by a circle) is 20% or less is preferable. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

Tabular grains have high covering power and require less silver to achieve the same density.

Therefore, tabular grains are preferably used from the viewpoint of reducing the amount of coated silver in light-sensitive materials for X-ray, which have a large amount of coated silver.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimie er Phys Photographic (Chimie er Phys Photography)
Photographic Emulsion Chemistry (Ph.

tographic Emulsion Chemises
try) (Focal Press, 1966), V, L, Ze Iikm
Making and Coating Photographic Emulsions (Making a) et al.
nd Coating Photographic
Emulsion) () γ-Calpress, 196
4), etc.).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3,704,130, No. 4,297.439, No. 4,276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, 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, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., using various synthetic hydrophilic polymeric materials such as single or copolymers. I can do it.

In addition to the general-purpose lime-treated ceratin, ceratin is also available in acid-treated ceratin and the journal of the Japanese Society of Scientific Photography (Bull).

Soc, Sci, Photojapan, Na 1
6, p. 30 (1966) may be used, or a hydrolyzate of seratin may be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroquine-1,3
゜5-triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-
propatool, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether, or vinyl polymers with vinylsulfonyl groups in their side chains) can quickly harden hydrophilic colloids such as gelatin and produce stable photographs. It is preferable because it gives characteristics. N-
Carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.) and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) also have a fast curing speed. Are better.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar 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. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbyl acid group can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic ring group (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635.7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743.510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613,
No. 615,641, No. 3,617,295, No. 3.
635. The combinations described in No. 721 are particularly useful.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrohencitriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole)
etc.: Mercaptopyrimidines: Mercaptotriazines; For example, thioketo compounds such as oxadolinthion, azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3.3
a, 7) Tetraazaindenes), Pentaazaindenes, etc.: Adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. I can do it.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The photographic material prepared using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for various purposes such as anti-irradiation or anti-halation.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is, from the support side, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in that order, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity.
The layer structure may further improve the graininess.

Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. It is also possible to have a configuration in which emulsion layers with different color sensitivities are inserted between emulsion layers with the same color sensitivities, and a reflective layer such as fine-grain silver halide is provided below the high-sensitivity layer, especially the high-sensitivity blue-sensitive layer. It may be provided to improve sensitivity.

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, it may be used in combination with an infrared-sensitive layer for pseudo-color photography or semiconductor laser exposure.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light.

In order to increase the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, claw discharge treatment, or ultraviolet irradiation treatment, or styrene-butadiene-based latex, vinylidene chloride-based latex, etc. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer.

In printing sensitive materials, in order to prevent deterioration of dimensional stability due to absorption of water by the support during development, it is desirable to use a hydrophobic polymer as an undercoat, and vinylidene chloride is preferably used.

Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dipping coating, roller coating, curtain coating, and extrusion coating can be used. U.S. Pat. No. 2,681,2 as appropriate.
No. 94, No. 2,761.791, No. 3,526,
Multiple layers may be applied simultaneously using coating methods such as those described in US Pat.

The present invention can be applied to various color and black and white photosensitive materials. Typical products include color film for general use or motion pictures, color reversal film for slides or television, color 1per, color positive film and color reversal 1per, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. This can be cited as an example. Research Disclosure, Ya/7/23(/
or by utilizing the three-color coupler mixture described in U.S. Pat. The present invention can also be applied to black-and-white photosensitive materials for X-rays and the like by using the black color-forming coupler described in No. /J Otsu. Films for plate making such as lithography film or scanner film, X-ray film for direct/indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, C0M or regular micro film, silver salt diffusion transfer type photosensitive materials and prints. The present invention can also be applied to out-type photosensitive materials.

When the photographic elements of the present invention are applied to color diffusion transfer photography, they may be of the peel-a-meat type or of the special color diffusion transfer type.
A-/13jA, 4tIr-33697, Japanese Patent Application Publication No. Sho-to-i3o≠O, and British Patent/, 330. ! λ≠
Integrated as described in the issue.
It is possible to adopt a structure of a film unit that does not require peeling, as described in Japanese Patent Application Laid-open No. 57-113≠j.

In either type of formant, the use of a polymeric acid layer protected by a neutralizing timing layer is advantageous in providing a wider range of processing temperatures. When used in color diffusion transfer photography, it may be added to any layer in the sensitive material, or it may be sealed in a processing solution container as a developer component.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, no-rogen-filled lamps, mercury lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flash pulp are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, lead titanium zirconate (PLZT), which is emitted from fluorescent substances excited by electron beams,
), etc., can be used as an exposure means in combination with a linear or planar light source. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The photographic processing of the light-sensitive material of the present invention can be carried out by, for example, Research Disclosure (Research Disclosure).
e) / 7 No. 2t-30 pages (RD-/7
Any of the known methods and known treatment liquids as described in 3) can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperature is normal/
Selected between r 0c and ro 0c.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroquine benzenes (for example), hydroquinone), 3
-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-
p-amine phenol and the like can be used alone or in combination. The developer generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc.
In addition, as required, solubilizing agents, color toners, development accelerators (e.g. μ-class salts, hydrazine, benzyl alcohol), surfactants, antifoaming agents, water softeners, hardeners (e.g. glutaraldehyde), viscosity It may also contain an imparting agent and the like.

For the light-sensitive material of the present invention and black-and-white reversal photographic processing, any known development processing method for forming a positive silver image by reversal development can be used. A known treatment liquid can be used. The processing temperature is normally selected between /+l''C and 60C, but it may be lower than /♂0C or higher than 0!0C.

Reversal development processing usually consists of the following steps.

7th development - washing with water - bleaching - cleaning - full-surface exposure - 2nd development: constant fixing - washing with water - drying.

The developer used in the black and white photographic processing of the first development can contain known developing agents. As developing agents, dihydroquinbenzenes (Tatoeba Hydroquinone), 3
-pyrazolidones (e.g./-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-
p-aminephenol), l-phenyl-3-pyrazolines, ascorbic acid, and U.S. patent θ17. ? 2
Heterocyclic compounds such as those described in No. 2, in which a / , x , j , μm tetrahydroquinoline ring and indoref ring are condensed, can be used alone or in combination.

In particular, it is preferable to use pyrazolidones and/or amine phenols in combination with dihydroquine benzenes. The developing solution generally contains other known preservatives, alkaline agents, PU buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. The light-sensitive material of the present invention usually contains sulfite ions as a preservative at 0.00%. /jmol/1 or more.

As for pH! ,! ~// is preferable, 2° in %! ~i
o and j are preferred.

The seventh developer contains no silver halide solvent such as Na5CN.
．． 3-tg/l is used.

As the second developing solution, a general black and white processing solution can be used. That is, the composition is obtained by removing the silver halide solvent from the first developer.

The pH of the second developer is good, especially the pH.

j~IO6! is preferred.

Bleaching agents such as potassium dichromate or cerium sulfate are used in the bleach solution.

Thiosulfates and thiocyanates are preferably used in the fixing solution, and may contain a water-soluble aluminum salt if necessary.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution to perform development. Among the developing agents, hydrophobic ones are described in Research Disclosure ITQ No. (RD-/A9ko♂), U.S. Patent No. 1,73.
They can be incorporated into the emulsion layer by various methods such as those described in U.K. Patent No. 213,263 or West German Patent No. 1j4t7.74j.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thio7anate, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phinidinediamine compounds are preferably used, representative examples of which are 3-methyl-μm amino-N,N-diethylaniline, 3 -Methyl-≠-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-kuamino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-≠-amino-N-xthiru-N
-β-methoxyethylanili/and sulfates thereof,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or anti-caking agents such as bromides, iodides, potassium zimidazoles, benzothiazoles or mercapto compounds. Generally, it contains agents such as agents. In addition, if necessary, preservatives such as hydroquine ruminos, dialkylhydroquine raminos, hydrazines, triethanolamine, triethylenediamine or sulfites, triethanolamine, organic solvents such as diethylene glycol, benzyl alcohol, etc. , polyethylene glycol quaternary ammonium salts, development accelerators such as amines, dye-forming couplers,
Competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as l-phenyl-3-pyrazolidone, tackifiers, aminopolycarbo/acids, aminopolyphospho/acids, alkylhonufo/acids, phosphonocarbo/
West German patent application for various chelating agents such as acids (
OLS) No. 2, 2, λ, 50, etc., may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydro-7 benzenes such as hydroquinone, l-phenyl-
3-Vyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as aminophenols such as methyl-p-aminephenol can be used alone or in combination.

Not only a color developing solution but also any photographic developing method may be applied to the light-sensitive material of the present invention. The developing agents used in the developer include dihydroquine benzene type developing agents, /
-Phenyl-3-pyrazolidones, todihydroquine benzenes, p-amine phenolic developing agents, etc. The photosensitive material of the present invention may also be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and No. hydrokino 7.

In the above, examples of dihydroquine benzene developing agents include 1, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,
Examples include 3-dichlorohydroquinone, λ,j-dimethylhydroquinone, and examples of l-phenyl-3-pyrazolidone-based developing agents include /-722-3-pyrazolidone,
μ1μm dimethyl/-phenyl-3-birasolid/,
Hiro-Hydrox/Methyl-≠'-Methyl-/Phenyl-3
-pyrazolidone, ≠, 4t-dihydroxy/methyl-/-
Phenyl-3-pyrazoliton, etc., and p-amine phenol developing agents include p-amine phenol, N
-Methyl-p-aminone enol and the like are used.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer.

As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, jetanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to t, r or more, preferably 5 or more.

The developer solution may also contain organic compounds known as anticapri agents or development inhibitors. Examples include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitro(nzoto-I/azoles, mercaptotetra-1-a)
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxacyly/thiones; azaindenes, such as triazaindenes, tetrazaindenes (especially ≠-hydroxy Replacement (/, J
, ja.

7) Tetrazaindenes), tetrazaindenes; Henze/thiosulfonic acid, benzenesulfinic acid,
Examples include benzenesulfonic acid amide and sodium λ-mercabutobenzimidazole-sulfonate.

The developer that can be used in the present invention may contain noboralkylene oxide as a development inhibitor, as described above. For example, polyethylene oxide with a molecular weight of 100 to 10,000 is used. It can be contained in the range of /~/Og/l.

It is preferable to add water softeners such as nitrilotriacetic acid, ethylene diamino tetraacetate, triethylenetetraamino, xaacetate, and diethylenetetraamine to the developer that can be used in the present invention.

The developing solution used in the present invention includes a compound described in JP-A No. 4-U+J≠7 as a silver stain prevention agent, a compound described in JP-A-22-272ZJ1 as an agent for preventing uneven development,
As a solubilizing agent, the compound described in Japanese Patent Application No. 1 O-io97≠3 can be used.

The developing solution used in the present invention contains a buffering agent.
Boric acid described in /-21701, JP-A-Sho-93≠3
The saccharides described in 3 (e.g. sucrose), oxidiums (
For example, phenols (eg, sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), etc. are used.

Various compounds may be used as the development accelerator used in the present invention, and these compounds may be added to either the sensitive material or the processing solution.

Preferred development accelerators include amide compounds, imidazole compounds, imidazole compounds, phosphonium compounds, sulfonium compounds, hydrazine compounds,
Examples include thioether compounds, thione compounds, certain mercapto compounds, menion compounds, and thiocyanates.

This is especially necessary for rapid development processing in a short period of time. It is desirable to add these development accelerators to the color developing solution, but depending on the type of accelerator or the position on the support of the photosensitive layer to be accelerated, it may be added to the photosensitive material. can. It can also be added to both the color developing solution and the photosensitive material. Furthermore, depending on the case, a pre-bath for the color developing bath may be provided and the additive may be added therein.

Amine compounds useful as amine compounds include both inorganic amines and organic amines, such as hydroxylamine. The organic amine can be an aliphatic amine, an aromatic amine/, a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine, primary, secondary and tertiary amines, and all perammonium compounds. It is valid.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include compounds of polyvalent metals such as iron (I), cobalt (III), chromium (■), and copper (I[), peracids,
Quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferrin anide; dichromate: iron (II [
) or organic complex salts of Copal BII [), such as aminopolycarmenic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-diaminony-propanoltetraacetic acid, or citric acid,
Complex salts of organic acids such as tartaric acid and malic acid; persulfates: manogates; nitronophenols, etc. can be used. Among these, ethylenediaminetetraacetic acid iron (■) salt,
Diethylenetriaminepentaacetic acid iron (In) salts and persulfates are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(II[) complex salt is particularly useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in the following specification. U.S. Patent No. 3. ♂q3. RZR, West German patent number 1
．． No. 290,1/2, No. 2,069゜qrr, No. 3273 of the same year, No. 3-17131 of the same year, No. 374 of the same year.
T/f issue, same! 3-4j732, same! 3-7j Ako 3
Same issue! 3-ta j430, same j3-9!63/no., same ta 3-1011-32, same j3-/ko ≠ Hiro 2 Hiro, same! Compounds having a mercapto group or a disulfide group described in No. 3-7≠/623, No. 2A, Research Disclosure No. A17129 (July 7R), etc.: JP-A-5O-iaoiλ Thiazolidi/derivatives as described in No.
ot issue, JP-A-12-20132, same! 3-3273
Thiourea derivatives described in the evening issue, US Patent No. 3,7ot, sti: West German Patent No. 1.1+27,7/! No., JP-A-61-/Otsu λ3! Iodide described in No. 9; West German Patent No. 9z
6. ≠IO No., same, 74Lf, ≠polyethylene oxides described in No. 30; Special Publication Showa 4t! - Polyamine compound described in No. 1Jt; Other times Kaisho ≠ Tar ≠ 24t3
μ issue, same μter 69A≠≠ issue, same j3-9μ927 issue,
Same thing≠-3j727, same thing j-26! Ot issue and the same! The compounds described in r-/A39Hiro0 and iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. ♂93. ? ! r, West German Patent No. 7゜290.112, JP-A-Sho! 3-ta! Compounds described in No. t30 are preferred. Furthermore, US Patent No. ! λ♂
Compounds described in No. 3 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thionanates, thioureas of thioether compounds, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carmenyl bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides and anti-piping agents that prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardening agents can be added as necessary. Or Photography Inc. Science and Engineering magazine by West (L, E, We
st, Phot, Sci, Eng,), Volume 4,
Compounds described in n→~3j Tabezi (/ri 45) etc. may be added. The addition of chelating agents and anti-piping agents is particularly effective.

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. Furthermore, instead of the water washing process,
-1f≠A multistage countercurrent stabilization treatment process as described in No. 3 may be implemented. In the case of this step, 2 to 9 countercurrent columns are required. In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, the membrane p
Various buffering agents (e.g., borate, metaborate, borax, salt, carbonate, potassium hydroxide, sodium hydroxide) for adjusting H (e.g., pH 3 to 3), IJum, anomonia Water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid/
Typical examples include aldehydes such as formalin (used in combination with acids, etc.) and formalin. In addition, chelating agents (inorganic/acid, aminopolycarbo/
acids, organic phosphoric acids, organic phosphonic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc.), fungicides (benzointhiazolinone, irithiazolone, 4-thiazolinebensimitasol, halogenated phenols, sulfanilamide, benzotriazole, etc.) ), surfactants, optical brighteners, hardeners, and other various additives may be used, and two or more compounds having the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent.

For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342.599, Research Disclosure No. 14850 and US Pat. No. 15159
In addition to the Schiff base-type compounds described in JP-A No. 13924, the metal salt complexes described in U.S. Pat. No. 56-6235, No. 56-16133, No. 56-59232, No. 5
No. 6-67842, No. 56-83734, No. 56-8
No. 3735, No. 56-83736, No. 56-8973
No. 5, No. 56-81837, No. 56-54430,
Examples include various salt-type precursors described in No. 56-106241, No. 56-107236, No. 57-97531, and No. 57-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are JP-A Nos. 56-64339, 57-144547, 57-211147, 58-50532, 5B-50536, 5B-50533, and 5B.
-50534, 58-50535 and 58-
115438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, for saving silver in photosensitive materials, West German Patent No. 2226.770 or U.S. Patent No. 3
Treatment using cobalt intensification or hydrogen peroxide intensification as described in , 674° 499 may also be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed as necessary, very generally, and even when it is a color photographic material for photographing.

In the present invention, the development processing time refers to the period from the time when the leading edge of the photographic light-sensitive material touches the developer to the time when the leading edge leaves the final drying zone in automatic processor processing.

The following method has been devised as a method for increasing the drying rate of photographic materials in an automatic processor, but the present invention is not limited thereto.

Method of detecting temperature and humidity and controlling drying temperature (Unexamined Japanese Patent Publication No.
-237659L Method of drying while dehumidifying (Unexamined Japanese Patent Publication No.
1-260444), a method of drying while irradiating far-infrared microwaves (JP 01-260445), a method using a heated conveyance roller (JP 0F-260448)
.

(Example) Example-1 Preparation of support (1) Corona discharge treatment was performed on a blue-dyed, biaxially stretched polyethylene terephthalate film with a thickness of 175 μm, and the first undercoating liquid was applied to the following coating amount. was applied using a wire bar coater and dried at 175° C. for 1 minute, and then applied in the same manner to the opposite side to form a first undercoat layer.

(First undercoat layer) 0 Butadiene-styrene copolymer latex 0.16 g/b 0 2.4-dichloro-6-hydroxy-8-triazine sodium trilam salt 3.2 g/b On the above first undercoat layer A second undercoat layer was provided on both sides by drying at 150° C. for 1 minute so that the coating amount was as follows.

0 Gelatin 0.08g/n (oc+
zu□0(CHzCHzO) +. H7,5 ■ / Bo 1 view 1 soil standing water making 12 contains 5 g of potassium bromide, 0.05 g of potassium iodide, 25.5 g of gelatin, 1,000 onychill HO (CH Ri! 5 (CH Ri! 5 (CH Add 2.5 cc of a 5% aqueous solution of Ri!OH and maintain it at 69°C, and add 1.8.35 g of sulfuric acid and 5.5 g of potassium bromide while stirring.
．． An aqueous solution containing 94 g of potassium iodide and 726 g of potassium iodide were added in 45 seconds using a double jet method. Subsequently, 2.9 g of potassium bromide was added, and then an aqueous solution containing 8.35 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition.

After this, 20cc of 25% ammonia solution, 50% N
After adding 10 cc of HaN Os and physically ripening for 20 minutes, 240 cc of IN sulfuric acid was added to neutralize.

Subsequently, an aqueous solution of 149.9 g of silver nitrate and an aqueous solution of potassium bromide were added over 40 minutes by a controlled double jet method while maintaining the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate at the end of addition was nine times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 2 cc of 1% potassium iodide aqueous solution was added.
5cc was added over 30 seconds. After this, increase the temperature to 35°
After lowering the temperature to 4°C and removing soluble salts by sedimentation,
74.5g of gelatin and 1.2g of Proxel at 0°C heating
g, and p) due to possible soda and potassium bromide! 6゜4
0, pAg was adjusted to 8.10.

After raising the temperature to 56°C, 6 sensitizing dyes with the following structure were added.
00g and 150g of stabilizer were added.

After 10 minutes, 2.4 μ of sodium thiosulfate pentahydrate, 140 μ of potassium thiocyanate, and 2.1 μ of chloroauric acid were added to each emulsion, and after 80 minutes, 2. It was cooled and solidified to form an emulsion.

In the obtained emulsion, 95% of the total projected area of all grains consisted of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more was 1.4 μm.
, the standard deviation was 15%, the average thickness was 0.190 μm, and the aspect ratio was 7.4.

A coating solution was prepared by adding the following chemicals per mole of silver halide to the emulsion of so, e Oja.

・Polymer latex (poly(ethyl acrylate/methacrylic acid) 97/3) 25.0g ・Hardening agent 1.2-bis(sulfonylacetamide) ethane Coating amount as shown in Table 1 ・26-bis(hydroxyamino)-4 -Diethylamino-1,3,5- Sodium triazine polyacrylate (average molecular weight 41,000) 80■ 4,0g ・Polystyrene sulfonate tyrium (average molecular weight 600,000) 1,0g The surface protective layer of each component was prepared so that the coating amount was as shown below.

Table mλ-gelatin polyacrylamide (average molecular weight 45,000) - Sodium polyacrylate (average molecular weight 400,000) - Sodium salt of pt-octylphenoxydiglyceryl butyl sulfonate - poly (degree of polymerization 10) Oxyethylene cetyl ether poly (weight degree 10) Oxyethylene poly (polymerization degree 3) Oxyglyceryl p-Oho J1 0.2 0, 02 0, 02 0, 7 0.035 Cutyl phenoxy ether 0. 01・CsF+
ySOsK 0. 003C
3H'1 * CJ + ts (hN4cHt masu←CHJySOJ
a O,OOIC5H?・CsF + tsOJ (CHxCHgOhTHCHz
CHCHtO□H0,003 ・Polymethyl methacrylate (average particle size 3.5 μm) ・Poly (methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm) Antihaley silane (AH) layer 0,025 0.020 According to Table 1, an AH layer, an emulsion layer and a surface protective layer were coated on a support in this order and dried to obtain photographic materials 1-1 to 1-4.

X-ray sensitometry was performed by applying Fuji Photo Film ■CRENEX Orthoscreen HR-4 to both sides of the photographic material using a cassette. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After exposure, automatic processor processing 1-1 was performed using the following developer and fixer.

Made by 51J1 old λ1 Dry to Dry processing time 45 seconds (If an undried sample was obtained, it was air-dried after processing.

) The developer and fixer used had the following compositions.

(Developer) Potassium hydroxide Potassium sulfite Sodium bicarbonate Borate diethylene glycol Ethylene diamine Tetraacetic acid 5-Methylbenzotriazole Hydroquinone Glacial acetic acid triethylene glycol 5-Nitroindazole I-Phenyl-3-pyrazolidone Glucuraldehyde (50W to 7W t% ) Add sodium metabisulfite and potassium bromide water (fixer) Ammonium thiosulfate 9g 44.2g 7,5g 1,0g 2g 1,7g 0.06g 5g 8g 2g 0.25g 2,8g 9.86g 12.6g 3.7g 1.01 (70wt/vo1%) 20(ld Ethylenediaminetetraacetic acid disodium dihydrate 0.02g Sodium sulfite 15g Boric acid
10g sodium hydroxide
6.7g glacial acetic acid
15g aluminum sulfate 10
g Sulfuric acid (36N) Add 3.9g water to make a total volume of 1j! (The pH was adjusted to 4.25.) The MTF was measured using a combination of R-4 screen and automatic processor processing (as described above).It was measured with an aperture of 30 μm x 500 μm, and the spatial frequency was 1, 0. cycle/
Using the MTF value of (2), the optical density is 1. Evaluation was made in the O section.

Evaluation of drying property The film was subjected to automatic processor processing 1-1.2 with a size of 24.5 x 30.5 CII, and the dry state was confirmed by touching the film immediately after it came out of the drying zone. The results are summarized in Table-1. The evaluation criteria are as follows.

O...It's dry enough.

x: The resulting film is damp and has not been sufficiently dried.

XX...The film that comes out is wet, and the films adhere to each other.

Automatic processor processing 1-2 Incubation processing was carried out at 50% relative temperature. The total hydrophilic colloid layer thickness of the photographic material was first measured, and then each sample was immersed in distilled water at 21° C. for 3 minutes. Then, the change in thickness was measured.

The thickness was measured by freezing the sample in liquid N2 and observing its cross section with a scanning electron microscope equipped with a liquid N2 stage.

Dry to Dry processing time: 29 seconds The developer and fixer were prepared in the same manner as in automatic processor processing 1-1.

Evaluation of Swelling Percentage Seven days after coating a photographic light-sensitive material that had not been subjected to photographic processing, the swelling percentage was measured. For 3 days, the temperature was 38°C, and the first layer of undercoat of the following formulation -■ and the formulation -■
A second layer of base coat was applied in sequence.

Prescription - 1st undercoat layer Aqueous dispersion of copolymer of vinylidene chloride/methyl methacrylate/acrylonitrile/methacrylic acid (90/8/1/1 weight ratio) 15 parts by weight 24-dichloro-6-hydroxy-s-triazine 0.25 Polystyrene fine particles (average particle 3μ) 0.05 #Compound-
■ Add 0.02 water
100 l Additionally, 10% by weight (7) KOH
The coating solution was adjusted to pH=6 and dried at a temperature of 180.
The coating was applied for 2 minutes at °C so that the dry film thickness was 0.9μ.

Compound-■ Compound-■ Prescription-〇 Undercoat 2nd layer gelatin 1 part by weight Methyl cellulose 0.05 #Compound-■
0.02 〃C1! H! 5O(CHIC
H*0) I6B 0. 03 7 compound-■
3.5 X 10-” ~acetic acid
0.2 Add water
100〃Dry this coating solution at a temperature of 170℃2
The amount of gelatin was applied to birch in 1 minute to give a gelatin content of 0.08 g/m2.

The compound HO(CO(CHri4CONH(CHriIN-(CHl
h-NHjH・C2HI llOH HzC1 The following formulation -
The conductive layer (■, -■) and the adhesive layer were undercoated.

Prescription - ■ Conductive layer Snow/Sb (9/1 weight ratio, average particle size 0.25μ
) 300■/Pogelatin
170 Compound bite
7 Sodium dodecylbenzenesulfonate salt 10 Sodium dihexyl-α-sulfosuccinate salt 40 Sodium salt of polystyrene sulfonate 9 Prescription - Back layer gelatin 2.9 g/compound -
■ 10g/idodecylbenzenesulfonic acid sodium salt 70-dibenzyl-α-sulfosuccinate sodium salt 151.2-bis(
Vinylsulfonylacetamido)ethane 150 #Ethyl acrylate latex (average particle size 0.05μ) 500 #Perfluorooctane sulfonic acid lithium salt 10 #Silicon dioxide fine powder particles (average particle size 4μ, pore diameter 170, surface area 300M/g) ) 35 Furthermore, the following coating was applied to the opposite side.

Emulsion A was prepared using the following solutions (1) and (2) in the following manner.

Liquid I: 600 Id of water, 18 g of gelatin, pH 3.0 Liquid: 200 g of AgNOs, BOOd of water 1) Emulsion A
(Br 1 mol%, particle size 0.20μ, Rh 1.0
xlO-'mol 1 molAg)■, liquid-liquid: KBr 1.4
g, NaCl176 g, (NHa) JhC1b
4 ■, 800 m of water in ■ liquid kept at 140°C ■,
Solution (1) was added by simultaneous mixing on both sides for 20 minutes while maintaining a constant speed. After removing the soluble salts from this emulsion using a conventional method well known in the art, gelatin was added to the emulsion to obtain a stable emulsion without chemical ripening.
,3,3a,7-thitraazaindene was added. The average grain size of this emulsion is 0.20μ, and the emulsion yield is 1k.
g, and the amount of gelatin contained was 45 g. A hydrazine compound (Hz) was added to this emulsion at 4×10-' mol 1 mol A.
An emulsion was prepared by adding g.

After adding an ultraviolet absorber (UV absorber) to 1100 W/m2, the solid content of polyethyl acrylate latex was 30 wt to gelatin.
% added as a hardening agent, 1,3-vinylsulfonyl-
2-Add the amount of propatool listed in Table-2 and apply the amount of silver 2.
The amount of gelatin coated was as shown in g/po Table 2.

On top of that, a protective layer containing 120 g/n of yellow dye to improve safelight safety was coated with 0.9 g/n of gelatin. World patent W08 B104794 Examples 1 to 7 using dyes as the silane layer (AH layer) as shown in Table-2
A dispersion dispersed in the same manner as above was added until the gelatin coating amount was 0.
It was coated at a concentration of 30 g/m2.

Photographic materials 2-1 to 2-16 were produced as described above.

The following was performed on photographic materials 2-1 to 2-16.

■ This sample [Phase] Halftone original ○ Transparent or semi-transparent pasting base ○ Line drawing original ■ Original composition with transparent or semi-transparent pasting base Dainippon Screen from the [F] side ■ P-607 ultra-high pressure mercury lamp Using ORC-CHM-1000, each sample was exposed to the same number of seconds by applying a neutral density filter (ND filter) and adjusting the exposure amount. Developing machine processing 2
-1 was performed to evaluate the image quality of the extracted characters. Note that CR-F1 was used as the fixing solution.

Automatic developer processing 2-1 Dry to Dry processing time: 45 seconds (If an undried sample was obtained, it was naturally dried after processing.) The composition of the developer used is shown below.

Developer A Hydroquinone 45.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18.0g Potassium hydroxide
55.0g 5-sulfosalicylic acid
45.0g boric acid 2
5.0g Potassium sulfite 110.0g
Ethylenediaminetetraacetic acid disodium salt 1.0g Potassium bromide 6.0g 5-methylbenztriazole 0.6gn-Butyl-jetanolamine 15.0g Add water
1iV.

(pH = 11.6) What is the image quality of cut-out characters? When a manuscript is properly exposed so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return, a 30 μm wide character is reproduced. The image quality is very good. -Emphasis-free character image quality refers to the image quality that can only reproduce characters with a width of 150 μm or more when given the same appropriate exposure, and is poor character quality, with a sensory evaluation of 4 to 2 between 5 and 2. A rank was established. A value of 3 or higher is a practical level.

Evaluation of drying property The film was processed in an automatic processor 2-1.2 in a size of 24.5 x 30.5 C1l, and evaluated in the same manner as in Example 1.

Automatic processor processing 2-2 Dry to Dry Processing time 29 seconds (If an undried sample was obtained, it was naturally dried after processing.) The developer and fixer used were the same as those used in automatic processor processing 2-1. It was used.

Evaluation of swelling rate Evaluation was made in the same manner as in Example-1.

Example-3 A corona discharge treatment was performed on a 100 μm polyethylene terephthalate film stretched by two wheels, and coated with a wire bar coater to the following coating amount.
It was dried at 70°C for 1 minute.

(First undercoat layer) Butadiene-styrene copolymer latex (butadiene/methylene weight ratio = 31/69) 0.16 g/bo 02.4
-Dichloro-6-hydroxy-s-triazine sodium salt 4.28/po By drying the second undercoat layer at 175°C for 1 minute on the first undercoat layer in the following coating amount. Established.

O gelatin 0.08g/BO OC,
, H250 (CHICHzO), @H7,5■/Preparation of emulsion (2) Solution I 75°C Solution II 35°C Solution 1 [I 35°C Solution ■ For room temperature solution ■, solution ■ and solution ■ was added for 5 minutes, and when octahedral particles with an average particle size of 0.10 μm were formed, the addition of liquids ① and ② was temporarily stopped, and per mole of silver,
11 each of sodium thiosulfate and tetrachloroauric acid salt
A chemical sensitization treatment was then carried out at 75°C for 60 minutes. Simultaneous addition of solutions ① and ② was continued again to the chemically sensitized core particles obtained in this way, and 5 minutes after restarting the addition of ②, solution ② was added over a period of 5 minutes to increase the pA of the mixed solution.
While adjusting the addition rate of Solution (2) so that the g value was 7.50, the entire amount of Solution (2) was added over 40 minutes at 75°C. In this way, the final average particle size is 0. A 28 μm cubic core/shell emulsion was obtained. After washing with water and desalting by the sedimentation method, the mixture was dispersed in an aqueous solution containing 90 g of inert gelatin. To this emulsion, 34 μ each of sodium thiosulfate and chloroauric acid tetrahydrate were added per mole of silver, and the pF and pAg values were adjusted to 8.9 and 7.0, respectively (at 40°C). , 75
Chemical sensitization was performed at °C for 60 minutes.

Antihalation (AH layer) Gelatin 0.3g/Bo0 compound 67.8■/BoCH10 Dye 01.3-Bis(vinylsulfonyl)-2-propatol 53.7■/Bo0 Phenoxyethanol 1.9 ■/po <Emulsion layer> 0 dye 0 dye C1hCHzSOJ CHzCHxSOY 48.5g/nucleating agent (compound ■) <Protective layer> Bonyl-N-propylglycine potassium salt 5. The AH layer, the opalescent layer and the protective layer were coated on the support in this order and dried to obtain photographic materials 3-1 to 3-4.

Evaluation of photographic performance Imagewise exposure was carried out from the emulsion coated surface under a safety light for 10-3 seconds through a continuous density wedge using a MARK-It xenon flash spectrophotometer manufactured by E, G, & G, USA. .

General-purpose processing liquid for microfilm (FRCemi, USA)
Automatic processor processing 3-1 was carried out under the following conditions using PR-537 developer (manufactured by Cals Inc.).

The results are shown in Table 3.

17] Display results Evaluation of swelling rate Shown in 3.

Evaluation was made in the same manner as in Example-1.

Evaluation of sharpness Sharpness was evaluated by MTF. The photographic material was exposed to white light for 1/100 seconds using an MTF measurement wedge, and subjected to the automatic processor processing 3-1 described above.

The MTF was measured using an aperture of 400 x 2 μm, and the MTF value at a spatial frequency of 20 cycles/h was used to evaluate the area where the optical density was 1.0.

The results are shown in Table-3.

Evaluation of drying property The above-mentioned automatic processor treatment 3-1 was carried out, and evaluation was made according to the evaluation criteria of Example 1.

(Effects of the Invention) According to the present invention, a silver halide photographic light-sensitive material having excellent sharpness and drying properties can be provided, and the light-sensitive material can be rapidly processed in 45 seconds or less.

Claims (5)

[Claims] (1) In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a solid dispersed dye and at least one silver halide emulsion layer on a support, the total amount of hydrophilic colloid coated on one side of the light-sensitive material is 2.5 g/m^2 or less, and the total hydrophilic colloid layer is hardened in an amount sufficient to cause the total hydrophilic colloid layer swelling to be less than 200 percent. Photographic material. (2) the entire hydrophilic colloid layer is hardened in an amount sufficient to reduce the swelling of the hydrophilic colloid layer to less than 170 percent;
Silver halide photographic material according to 2. (3) Total hydrophilic colloid coating amount is 2g/m per side
Claims 1 to 3 characterized in that ^2 or less
The silver halide photographic material described above. (4) A development processing method, characterized in that the silver halide photographic material according to claims 1 to 4 is used in a development process of 45 seconds or less. (5) A development processing method, characterized in that the silver halide photographic material according to claims 1 to 4 is used in a development process of 30 seconds or less.