JPH0414035A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance dyeability and decolorability of the photosensitive material and a state of a coating surface by specifying the average particle diameter of solid disperse dye particles and the variation coefficient of a particle size distribution. CONSTITUTION:This photosensitive material is provided with a hydrophilic colloidal layer containing the solid disperse dye particles (A), such as an antihalation layer, and the dye A, such as a compound represented by formula I, has an average particle diameter of 0.1 - 0.6 mmu and a variation coefficient of <=50%, and it is preferred to carry out development processing of this photosensitive material within 45 sec, especially, 35 sec.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inert and easy to use in the photographic processing process. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye that is rapidly decolorized and/or eluted.

(Prior Art) In silver halide photographic materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

It is based on the fact that light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enters the photographic emulsion layer again. Between the photographic emulsion layer and the support, for the purpose of preventing image blurring, that is, halation,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of multilayer photosensitive materials, an antihalation layer may be placed between each layer.

Furthermore, in X-ray photosensitive materials, a colored layer may be provided as a loss-over cut filter to reduce crossover light and to improve sharpness.

Deterioration of image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.

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

(1) Must have 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 emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

(3) In the photographic processing process, no harmful coloration remains on the photographic material after being bleached or dissolved and removed.

In particular, in recent years, it has been desired to complete the development process of photographic materials as quickly as possible in order to cope with the increase in the number of photographic images and also due to the social situation of obtaining information quickly.

Therefore, it is essential that the dye in the colored layer does not remain after the rapid development process.

Yes, for selective coloring of a specific hydrophilic colloid layer (there are some methods. A hydrophilic polymer containing a moiety with an opposite charge to the dye ion is made to coexist as a mordant in the hydrophilic colloid layer, and this and dye molecules The most frequently used method is to localize the dye in a specific layer by interaction with the dye (considered as charge attraction and hydrophobic bonding).

However, when mordanting methods are used, when the dyed layer and another hydrocolloid layer come into wet contact, it often occurs that some of the dye diffuses from the former to the latter. Such diffusion of the dye naturally depends on the chemical structure of the mordant, but also on the chemical structure of the dye used.

Further, when a polymeric mordant is used, residual coloring is particularly likely to occur on the light-sensitive material after photographic processing, especially photographic processing in which processing time is shortened. This is because although the binding force of the mordant to the dye becomes considerably weaker in an alkaline solution such as a developer, some binding force still remains, so the dye or reversible decolorization product remains in the layer containing the mordant. This is thought to be because.

In addition, as another means for fixing the dye in a specific layer in a photographic light-sensitive material, JP-A-56-12639 and JP-A-55-15535
No. 0, No. 55-155351, No. 52-92716, No. 63-197943, No. 63-27838, No. 64-40827, European Patent 0015601B
No. 1, No. 0276566A1, International Application Publication No. 8810
It has been proposed to have the dyes present in dispersed solid form as disclosed in US Pat. No. 4,794.

(Problem to be solved by the invention) However, simply dispersing solid dyes contains dyes with large particle sizes, so the particle sizes are small (and compared to disperse dyes, which have almost uniform particle sizes, the appearance is The absorbance decreases.For this reason, if you do not add more than necessary to the colored layer, the absorbance of the colored layer will decrease, reducing the filter effect and antihalation effect.Furthermore, depending on the dye, the surface condition of the colored layer may deteriorate. It has many drawbacks, such as the filter effect and antihalation effect not being uniform, or if the colored layer is on the top layer, the dye may peel off due to friction, and the surface gloss may deteriorate.

Furthermore, in the rapid processing process that has been required in recent years, solid dyes with relatively large particle sizes require a longer time to be decolorized or dissolved and removed, so colored layers containing large particles may remain colored or stain after processing. There is something. In order to solve this problem, it has been proposed to use dyes that are highly reactive with sulfite ions, but in this case, the stability in the photographic film is insufficient, and the concentration may decrease over time, resulting in the desired The disadvantage is that the photographic effect cannot be obtained.

(Objects of the Invention) Therefore, the first object of the present invention is to provide silver halide in which the hydrophilic colloid layer is colored with a dye that is irreversibly decolorized by photographic processing and does not have an adverse effect on the photographic properties of the photographic emulsion. An object of the present invention is to provide photographic materials.

A second object of the present invention is to create a hydrophilic colloid layer in which only the desired hydrophilic colloid layer is sufficiently selectively dyed with a dye, and which also has excellent decolorizing properties even in rapid processing with a development processing time of 45 seconds or less. It is an object of the present invention to provide a silver halide photographic material having the following properties.

A third object of the present invention is to provide a silver halide photographic material having a colored hydrophilic colloid layer with excellent coating surface condition.

A fourth object of the present invention is to provide a hydrophilic colloid layer in which only a desired hydrophilic colloid layer is dyed with a dye, and which has an excellent filter effect, antihalation effect, or sensitivity adjustment effect of a photosensitive emulsion relative to the weight of the dye. An object of the present invention is to provide a silver halide photographic material having the following properties.

(Means for Solving the Problems) The object is to provide a silver halide photographic material having at least one hydrophilic colloid layer containing a solid-dispersed dye, in which the dye has an average particle diameter of 0.1 μm to 0.6 μm.
is within the range of , and the coefficient of variation of particle size distribution is 50%.
This was achieved by a silver halide photographic material having the following characteristics. Here, the coefficient of variation is a value expressed as S/d, where d is the average particle diameter of the dye and S is the standard deviation of the particle diameter.

First, the dye used in the present invention will be described.

The dye used in the present invention is covered by International Patent WO3810479.
(I) to (■) shown below in Tables I to X1 of No. 4, and others are used.

General formula (I) General formula (Vl) General formula (■) A=C-(CH=CH÷)Q General formula (II) General formula (II[) A=L, =(L2=L3). -A' General formula (EV) A-(I-R2)t-=B General formula (V) (In the formula, A and A' may be the same or different, each represents an acidic nucleus, and B is 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 R2 each represent an alkyl group, an aryl group, an anru group, or a sulfonyl group, and R and R2 may be linked to form a 5- or 6-membered ring.

R1 and R6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkokino group, or a halogen atom, and R4 and R5 each represent a hydrogen atom, or R1 and R, or R2 and R5 are connected to form a 5- or 6-membered ring. Represents a group of nonmetallic atoms necessary to form . LI, R2 and R3 each represent a methine group.

m represents 0 or 1, n and q each represent 0, l or 2, p represents 0 or 1, when p is 0, R5 represents a hydroxy group or a carboxyl group, and R4 and Rs are Represents a hydrogen 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 has at least one dissociative group having a pKa in the range of 4 to 1) in a mixed solution of water and ethanol in a volume ratio of 1:1. ) First, general formula (I) or ■
) will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbylic acid, thiobarbital acid, indandione, pyrazolopyridine. Or represents 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, thiovilane, 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 1 in a mixed solution of water and ethanol in a volume ratio of 1 to 1 will substantially dehydrate the dye molecule at pH 6 or below. There are no particular restrictions on the type and substitution position on the dye molecule as long as it makes the dye molecule insoluble and makes the dye molecule substantially water-soluble at pH 8 or above, but preferably a carboxyl group, a sulfamoyl group, or a sulfonamide group. , a hydroxy group, and a more preferred one is a carboxyl group. The dissociative group may be substituted not only directly on the dye molecule, but also 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, 3,5dicarboxyphenyl, 3-carboxyphenyl, 2,5 -dicarboxyphenyl, 3-ethylsulf7moylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2°4.6-)rihydroxyphenyl, 3-benzenesulfonamidophenyl, 4-(p-cyamibenzene) 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, 2,5-disulfamoylphenyl, carboxinmethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl, etc. I can do it.

The alkyl group represented by R, R, 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,, 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., halogen atoms such as chlorine bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group (e.g., methoxy,
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 groups represented by 1 and R2 include the groups and alkyl groups (eg, methyl, ethyl). ].

The acyl group represented by R1 or R2 is preferably an acyl group having 2 to IO carbon atoms, and includes, for example, acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl, benzoyl, and the like. R, or R
Examples of the alkylsulfonyl group or arylsulfonyl group represented by 2 include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, 0
-carboxybenzenesulfonyl and the like.

The alkoxy group represented by R8 or R1 has 1-1 carbon atoms.
0 alkoxy groups are preferred, and examples include groups such as methoxy, ethoxy, n-butoxy, n-octoquine, 2-ethylhexyloxy, isobutoxy, and isopropoxy. Examples of the halogen atom represented by R3 or R1 include chlorine, bromine, and fluorine.

Examples of the ring formed by linking R3 and R4 or R2 and R5 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 ri may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, I-oxo-7-chloroheptyl), arylcarbonyl group (arylcarbonyl group that may be substituted, e.g. 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, decyloxy Carbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-
Methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)ethoxy]ethoxycarbonyl), amyloxycarbonyl group (optionally substituted amyloxy A carbonyl group, such as fenoquine carbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenoquinecarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2.4-
di(t-amyl)phenoxycarbonyl), carbamoyl group (carbamoyl group which may be substituted, for example, carbamoyl group ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-promophenylcarbamoyl, 4-
Chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3
-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di(t-amyl)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbamoyl)phenylcarbamoyl, 3(hexyloxycarbonyl)phenylcarbamoyl), Sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl)
, represents a sulfamoyl group (a sulfamoyl group that may be substituted, for example, sulfamoyl, methylsulfamoyl).

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

■ ■ ■ ■-20 ■-22 ■-25 ■ ■-17 ■-18 ■ ■ ■ ■ FI OOH ■ I-1 CH.

■ ■ ■-36 ■ ■ -t ■3 ■3 ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ OOH OOH lll-16 ■ ■ ■-19 1) 1 Shire 3 ■ ■ ■ OOH ■-20 ■ ■-22 ■ ■ OOH ■ CH.

0OH COOI( CH.

■-30 ■-32 ■ ■ ■ V-3 C, H5 C00I ( ■ ■ ■ V-4 V-5 V-7 ■ ■ ■ ■ H3 ■ ■ V-1 ■-14 ■ ■ ■ ■ 2H5 OOH Hs Cρ ■ I-1 N NH302CH3 l-2 OOH ■ ■ ■ N OOH OOH ■-12 ■-2 C OOH ■-3 ■-1 ■-4 ■-5 OOH The dye used in the present invention is based on international patent WO3810479.
No. 4, European Patent EPO 274723A1, No. 2
No. 76.566, No. 299,435, JP-A-52-9
No. 2716, No. 55-155350, No. 55-155
No. 351, No. 61205934, No. 48-68623
No. 25'27583, U.S. Patent No. 3486897
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 dye in the dispersion of the invention has an average particle size of 0. It exists as a fine solid with a particle size distribution coefficient of variation of 50% or less, ranging from 1 μm to 0.6 μm. Particularly preferably, the average particle size is 0. The dye has an average particle size of 1 to 0.5 μm, more preferably an average particle size of 0.5 μm. 1~0.5μ
The dye dispersion has a coefficient of variation of 35% or less in m.

For methods of dispersing dyes, see International Application Publication (WO)
88104794, European Patent (EP) 02765
66Al, described in JP-A No. 63-197943, etc., or mechanically pulverized with a ball mill, sand mill, colloid mill, etc., stabilized with a surfactant and gelatin, and after dissolving the dye in an alkaline solution,
A method of lowering the pH and causing precipitation is used. However, the present invention is not limited to these methods.

In the present invention, when large particles are contained in the dispersion obtained by the above method, an operation for removing them is performed.

Centrifugation, filtration, etc. are used to remove large particles. Also preferably used is a method in which a dispersion containing large particles is stirred with a Polytron or DeSilver to pulverize the particles. However, the present invention is not limited thereby.

The amount of dye used is 1 to 1 per meter of area on the photosensitive material.
1000■ used, preferably 1-800+ per 1m
ng is used.

When the dispersed solid dye is used as a filter dye or antihalation dye, any effective amount can be used, but preferably it is used so that the optical density is between 0.05 and 7.3.5. . The addition time may be any step before coating.

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. Also, particles whose latent image is mainly formed on the surface (
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 obtained by dividing the standard deviation S by the diameter d in the distribution expressed by the diameter when the projected area is approximated as a circle) of 20% or less is preferable. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

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

tographique) (published by Ballmontel, 1
967), C.F.D.7 I:/ (G, F, D
uffin), Photographic Emulsion
Chemistry (Ph.

tographic Emulsion Chemises
try) (Focal Press, 1966), V. L. Zelikman
) et al., Making and Coating Photographic Emulsions (Making and C
oating Photographic Emuls
ion) (Focal Press, 1964).

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 sulfates; 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.

As for gelatin, in addition to the general-purpose lime-treated ceratin, acid-treated ceratin and the journal of the Japanese Society of Scientific Photography (Bull).

Soc, Sci, Phot, Japan), N1)l
Enzyme-treated seratin as described on page 6.30 (1966) may be used, or a hydrolyzate of gelatin 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-hydroxy-1,3
5-triazine and its sodium salt, etc.) and active vinyl compounds (l,3-bisvinylsulfonyl-2-
Property tools, 1. (2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether, vinyl polymers having a vinylsulfonyl group in the side chain, etc.) are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties. . N
-Carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.)
and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) are also excellent in their fast curing speed.

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 nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, caphthothiazole 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,
5- to 6-membered heterocyclic nuclei such as a 4-dione nucleus, a thiazolidic 2,4-one 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, aminostilbenzene compounds which are nitrogen-containing heteroartic ring nuclei groups and are substituted (for example, 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, chlorohenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl 5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthion;
Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3.3a
, 7) tetraazaindenes), pentaazaindenes, etc.; can be added.

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.

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.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods can be used, such as dip coating, roller coating, curtain coating, and extrusion coating. U.S. Patent No. 2,681,294 as appropriate
Multiple layers may be applied simultaneously by coating methods such as those described in US Pat.

The present invention can be applied to a variety of color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. It can also be applied to a direct positive color light-sensitive material using an internal latent image type silver halide emulsion which has not been fogged in advance, as described in JP-A-63-159847. Research Disclosure, Nα17123 (July 1978
or by utilizing the black-forming couplers described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136, etc. The present invention can also be applied to black and white photosensitive materials for X-rays and the like. Plate-making films such as lithography film or scanner film, X-ray film for direct/indirect medical use or industrial use, black and white film for photography, black and white photographic paper, C0M or regular microfilm, silver salt diffusion transfer type photosensitive materials, and The present invention can also be applied to print-out type photosensitive materials. In particular, the photosensitive material of the present invention is advantageous in processing in a system in which the development processing time is extremely shortened, and is therefore preferably applied to black and white photosensitive materials. The effect becomes noticeable when applied to photosensitive materials that require particularly rapid processing, such as film for plate making, X-ray film, micro film, and film for COM.

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, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired flashbulbs 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, fluorescent surfaces (CRTs, fluorescent screens, etc.), liquid crystals (LCDs) emitted from phosphors excited by electron beams, X-rays, etc.
) and lanthanum-doped lead titanium zirconate (P
It is also possible to use an exposure means that combines a linear or planar light source with a micro-shutter array using LZT) or the like. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

Photographic processing of the light-sensitive material of the present invention can be carried out by, for example, Research Disclosure.
ure) No. 176, pages 28-30 (RD-17643)
Any of the known methods and known treatment liquids as described in can be applied. This photo processing is
Depending on the purpose, either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing) may be used. Processing temperature is usually 18℃
and 50'C.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p
-Aminophenol and the like can be used alone or in combination. The developer generally contains other known preservatives,
Contains alkaline agents, pH buffering agents, antifogging agents, etc., and further contains solubilizing agents, color toning agents, development accelerators (e.g., quaternary salts, hydrazine, Hensyl alcohol), surfactants, antifoaming agents, It may also contain water softeners, hardeners (eg, glutaraldehyde), viscosity-imparting agents, 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. Processing temperature is usually from 18℃ to 658℃
but lower than 18°C or 656°C
The temperature may exceed .

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 No. 169 (RD-16928) and U.S. Patent No. 2,73.
No. 9,890, British Patent No. 813,253 or West German Patent Application.

They can be incorporated into the emulsion layer by various methods such as those described in US Pat. No. 547.763.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, nucleating 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. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl- 4-amino-N-ethyl-Nβ
-Hydroxylethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. 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 antifoggants such as bromides, iodides, benzimidazoles, benzodeazoles or mercapto compounds. It is common to include. Also, if necessary, preservatives such as hydroxylamines, dialkylhydroxylamines, hydrazines, triethanolamine, triethylenediamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, Hensyl alcohol, etc. , polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers,
Competitive couplers, nucleating agents such as sodium holone hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids West German patent applications have been filed for various cattle rate agents such as
OLS) No. 2,622,950 and the like may be added to the color developer.

The photosensitive material of the present invention may be applied with not only a color developing solution (but also any photographic developing method).
- Phenyl-3-pyrazolidone type developing agents, p-aminephenol type developing agents, etc. These can be used singly or in combination (for example, 1-phenyl-3-pyrazolidones and dihydroxybenzenes, or p-aminophenols and dihydroxybenzenes). ) can be used. Further, the light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone.

In the above, examples of the dihydroquinbenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2.
There are 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc., and 1-phenyl-3-pyrazolidone type developing agents include 1-phenyl-3-pyrazolidone,
4.4-dimethyl-1-phenyl-3-pyrazolidone,
4-hydroxymethyl-4'-methyl-l phenyl-3
-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, etc. p-aminophenol developing agents include p-aminophenol, N-
Methyl-p-aminophenol 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 8.5 or higher, preferably 9.5 or higher.

The developer solution may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.: mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione, azaindenes, e.g. Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (]), 3.
3a.

7) Tetrazaindenes), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Examples include pensene sulfonic acid amide, 2-mercaptobenzimidazole-5 and sodium/lium sulfonate.

The developer that can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide having a molecular weight of 1,000 to 10,000 can be contained in a range of 0.1 to 10 g/l.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraamine, hexaacetic acid, diethylenetetraamine pentaacetic acid, etc. as a water softener to the developer that can be used in the present invention.

The developer used in the present invention includes a compound described in JP-A No. 56-24347 as a silver stain prevention agent, a compound described in JP-A-62-212651 as an agent for preventing uneven development,
As a solubilizing agent, the compounds described in Japanese Patent Application No. 60109743 can be used.

In the developing solution used in the present invention, a buffering agent is used.
Boric acid described in 2-186259, JP-A-60-934
Saccharides (e.g. sucrose), oximes (e.g. acetoxime), phenols (e.g.
5-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 amine compounds, imidazole compounds, imidacillin compounds, phosphonium compounds, sulfonium compounds, hydrazine compounds,
Examples include thioether compounds, thione compounds, certain mercapto compounds, isoion compounds, and thiocyanates.

In particular, these development accelerators are necessary for rapid development processing in a short period of time.It may be desirable to add them to the color developing solution, or depending on the type of accelerator, or on the support of the photosensitive layer to be accelerated. It can also be added to the photosensitive material depending on its position in the composition. 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.

Amino compounds useful as amino compounds include both inorganic amines and organic amines, such as hydroxylamine. Organic amines can be aliphatic amines, aromatic amines, cyclic amines, mixed aliphatic-aromatic amines or heterocyclic amines; primary, secondary and tertiary amines as well as quaternary ammonium compounds are all useful. be.

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 iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (n), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatol tetraacetic acid; Complex salts of aminopolycarboxylic acids such as acetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; manganates; nitrosophenols, and the like can be used.

Among these, ethylenediaminetetraacetic acid iron (III) salt,
Diethylenetriaminepentaacetic acid iron (I[I) salts and persulfates are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complexes are particularly useful both in stand-alone bleach solutions and in -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 U.S. Pat. No. 3,893,858, West German Patent Box 1.
．． ．． No. 290,812, No. 2,059°988, JP-A No. 53-32736, No. 53-57831, No. 37
No. 418, No. 5 L-65732, No. 53-7262
No. 3, No. 5195630, No. 53-95631, No. 51-104232, No. 53-124424, No. 5
3-141623, 53-28426, Research Fist Disclosure No. 17129 (July 1978), and other compounds having a mercapto group or disulfide group; Thiazolidine derivatives; Japanese Patent Publication No. 45-850
No. 6, JP-A-51-20832, JP-A-5I32735, U.S. Pat. No. 3,706,561;
Iodide described in No. 16235; West German Patent Box 966.41
Polyethylene oxides described in No. 0, No. 2,748,430; Polyamine compounds described in Japanese Patent Publication No. 45-8836; Others
No. 59644, No. 53-94927, No. 54-357
No. 27, No. 55-26506 and No. 58-1639
The compounds described in No. 40 and iodine and bromide 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 disclosed in U.S. Patent No. 3,893,858, West German Patent Box 1.290,
Compounds described in No. 812 and JP-A-5395630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 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, thiocyanates, thioureas of thioether compounds, and a large amount of iodides, but thiosulfates are commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl 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 Photographic Science and Engineering magazine by West (L, E, We
It is also possible to add compounds such as those described in J. St., Phot, Sci, Eng.), Vol. 6, pp. 344-359 (1965). The addition of chelating agents and anti-bacterial agents is particularly effective.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as that described in No.-8543 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 this stabilizing bath for the purpose of stabilizing images. For example, the membrane p
Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid) for adjusting H (e.g. pH 3-9) Typical examples include aldehydes such as formalin (using a combination of acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid,
Organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid,
phosphonocarboxylic acids, etc.), fungicides (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenol, sulfanilamide,
benzotriazole, etc.), surfactants, fluorescent brighteners,
Various additives such as hardening agents may be used, and two or more compounds for 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.

The development processing time of the present invention varies depending on the type of photosensitive material and processing conditions, but is usually 10 minutes or less.

In the present invention, rapid processing is preferably used in which the development processing time is 45 seconds or less. More preferably, the processing time may be 30 seconds or less.

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.

One way to increase the drying speed of photographic materials in automatic processors is to dry them while dehumidifying them (Japanese Patent Application Laid-Open No.
-260444), method of drying while irradiating with far infrared rays and micro-rays (JP-A-01-260445), method using a heated conveyance roller (JP-A-01-260448)
However, the present invention is not limited thereto.

(Example) Next, the present invention will be specifically explained based on examples.

Example 1 The following dye was dispersed as a solid by the following methods (1) to (4), and 0.14 g of the dispersed solid of the dye shown below was placed on an undercoated 180μ polyethylene terephthalate transparent support.
/i, Seratin 3 g/g and l as a hardening agent,
A film coated with 0.06 g/rrr of 2-bis(vinylsulfonylacetamido)ethane was prepared. Water 21.71nI! and TritonX-200° surfactant (TX-200°) (Rohm & Haa
2.65 g of a 6.7% solution (manufactured by S Company) was placed in a 60-screw bottle. 1.0 g of dye was added to this solution. Zirconium oxide (ZrO) beads 40J (2mm diameter)
was added, the lid was tightly tightened, the mixture was placed in a mill and dispersed for 7 hours, then mixed with a 12.5% aqueous seratin solution, bubbles were removed, and the beads were removed by rocking to obtain a dispersion.

(2) After diluting the dispersion obtained by the method (1) above with water, centrifuge it at 8000 rpm for 10 minutes, remove the sediment, and redisperse the suspension in Seratin to obtain a dispersion. Ta.

(3) The dispersion obtained by the method (1) above was heated with Polytron for 5 minutes.
Aggregates were broken down at 00 rpm for 5 minutes to obtain a dispersion.

(Dye) The volume average particle size and particle size distribution of each dispersed solid were measured using a Mastersizer (Malve).
(manufactured by rnInstruments Ltd.).

(Measurement of fixation rate) The prepared coated film was immersed in a phosphate buffer solution with a pH of 5.0.
After being immersed for a minute, the sample was rinsed with running water for 10 seconds, dried, and the absorbance was measured. The fixed rate was expressed as a percentage of the absorbance before treatment. It is desirable that the fixation rate be high in a neutral or weakly acidic region.

(Measurement of residual color rate) (A) The prepared coated film was coated with Menz at pH 10.0.
After immersing a solution of sodium sulfite dissolved at a ratio of 10 g/A in an el buffer solution for 45 seconds while stirring with air bubbling, the sample was rinsed in a 5% acetic acid aqueous solution for 5 seconds, then rinsed with running water and dried. , the absorbance was measured. The residual color rate was expressed as a percentage of the absorbance before treatment.

Since the conditions in which sodium sulfite is present in a high pH region are generally conditions closer to those of a developer, it is desirable that the residual color rate be lower.

(B) The prepared film was soaked in Menzel at pH 0.0.
10g/j of sodium sulfite in the buffer solution! The residual color rate was determined in the same manner as in (A) except that the sample was immersed for 10 seconds in a solution dissolved at a ratio of .

The spectral absorption spectrum, fixation rate, and residual color rate of each coated film were measured, and Table 1 shows the average particle diameter of the dispersion, the coefficient of variation of the particle size distribution, the maximum absorption wavelength of the coated film, the absorbance at the maximum absorption wavelength, and the fixation rate. The values of percentage and residual color percentage are shown.

As can be seen from Table 1, when using the dispersion of the present invention,
It can be seen that a colored layer with high absorbance can be obtained with the same coating amount, and a film with excellent antihalation effect, filter effect, etc. can be obtained.

Further, it is clear that the dispersions ①-① and ① of the present invention provide a fixation rate equivalent to that of ①-■, and also provide a good residual color rate that is superior to that of ①-■. In particular, when the time of immersion in an alkaline aqueous solution containing sodium sulfite is short, the coated product of the present invention is uniformly decolored. It is clear that the coatings of the present invention have a fast decolorization rate and are suitable for rapid processing.

Example 2 <Support> A biaxially stretched 100 μm polyethylene terephthalate film was subjected to corona discharge treatment, and coated with a wire bar coater to the following coating amount.
It was dried at 70°C for 1 minute.

(First undercoat layer) 0 Butadiene-styrene copolymer latex (ethane/styrene weight ratio 31/69) 0.16 g/I02.4
-Dichloro-6-hydroxy-8-) riazine sodium salt 4.2 g/rd (second undercoat layer) A second undercoat layer was applied on the first undercoat layer to have the following coating amount: 175 g/rd. It was prepared by drying at ℃ for 1 minute.

0 Gelatin 0.08g/mOC+J
2sO(CH2CH2O)+oH7, 5mg/rr?
Preparation of emulsion (1) Solution I 75°C Diethylthio)ethane solution II 35°C 2,5X10-' molar solution ■ 35°C solution ■ Add solution ■ and solution ■ to room temperature solution I at the same time for 5 minutes 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,
Sodium thiosulfate and chloroauric acid tetrachloride 1) each
A chemical sensitization treatment was then carried out at 75° C. for 60 minutes. Simultaneous addition of solution (1) and solution (2) to the chemically sensitized core particles thus obtained was continued again, and 5 minutes after the addition of solution (2) was resumed, solution (2) was added over a period of 5 minutes to increase the pAg value of the mixed solution to 7.50. The entire amount of Solution (2) was added over 40 minutes at 75° C. while adjusting the addition rate of Solution (2) so that the result was as follows. In this way, a cubic core/shell emulsion with an average grain size of 0.28 μm was finally 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 were added 34 μ each of sodium thiosulfate and chloroauric acid tetrahydrate per mole of silver, and the pAg values were adjusted to 8.
9 and 7.0 (40°C), then 60°C at 75°C.
Chemical sensitization treatment was performed for 1 minute.

Antihalation layer (AH layer)> 0 gelatin 0.3 g/I0 dye (■-2) 0 dye (I-33) ol, 3-bis(vinylsulfonyl)-2-propanol 53.7 g/bo The dye is the second
According to (■) to (■) in the table, the amount of seratin and the amount of dye were corrected and adjusted to the stated values using those dispersed in a solid state.

<Emulsion layer> 0OEt 61.4■/bo Compound ■ CJ5 (C1aso,.

Nucleating agent (compound ■) C, H6 CI (, C: C1 (wetting agent (compound O) <protective layer> The AH layer, emulsion layer, and protective layer were coated on the support in this order and dried to form photographic material 2-■ ~■ was obtained.The solid dispersion of the AH layer was 2
Dispersion method (1) and (3) of Example 1 for different types of dyes
Adjusted accordingly.

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 ■ xenon Flange sensitometer manufactured by E, G, &G, USA.

General-purpose processing liquid for microfilm (FRCemi, USA)
Automatic processor processing (1) was performed using Cals Inc. FR-537 developer under the following conditions.

Table 3 Automatic processor processing +1) Dry to Dry 40.5 seconds 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 treatment (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/M was used to evaluate the area where the optical density was 1.0.

Evaluation of residual color Photographic materials 2-1 to 2-2 were subjected to the same treatment (1) as in the above evaluation of photographic performance without being exposed to light.

The residual color after the treatment was sensory evaluated and the results are summarized in Table 4.

The following level classification was applied as evaluation criteria.

◎...No residual color bothers me at all.

○: There is a slight residual color, but there is no practical problem.

×...I'm concerned about residual color. There are practical problems.

X: The residual color is extremely bad, and it cannot be put to practical use.

The sensitivities of Photographic Materials 2-■ to 2-■ were the same, and there were no problems in practical use.

As is clear from Table 4, when the dispersion of the present invention is used, the dye decolorization is rapid (and there is no residual color at all).Also, the amount of dye is slightly small (the conventional dispersion has no sharpness). It can be seen that even if the dispersion of the present invention is used in an amount that cannot produce a sufficient amount, a photographic material with excellent sharpness can be obtained because the absorbance is large.

(Example 3) The following formulation on both sides of a biaxially stretched polyethylene terephthalate support with a thickness of 100 μm - 1st undercoat layer and formulation -
The second layer of undercoat (2) was applied in sequence.

Prescription - 1st layer of undercoat Aqueous dispersion of copolymer of vinylidene chloride/methyl methacrylate/acrylonitocle/methacrylic acid (90/8/1/1 weight ratio) 15 parts by weight 2.4-dichloro-6-hydroxy s-Triazine 0.25 〃Polystyrene fine particles (average particle size 3μ) 0.05” Compound-〇
Add 0.20” water
100 horns, add 10% by weight of KOH,
The coating solution adjusted to pH = 6 was dried at a temperature of 180°C for 2 minutes until the dry film thickness was 0. It was applied to a thickness of 9μ.

Compound - Add 100 parts by weight of water. Dry this coating solution at a temperature of 170°C for 2 minutes until the amount of gelatin is 0.16 g.
/lrr.

Compound ■ HO+C0(CHt)<CDNH(CH2)J-(CL
)2NfP arm, H-HCj2H2 HOH HICff Compound-〇υ Prescription-■Undercoat 2nd layer Gelatin 1 part by weight Methyl cellulose 0.05” Compound-〇
0.02”C1□H2,0(CH2CH20)I.H
O,031/ Compound -(a 3.5X10-""Acetic acid 0.2") A conductive layer and a back layer of the following formulations - (1) and (2) were coated on one side of the support thus obtained.

Prescription-■ Conductive layer 5nOt/Sb (9/1 weight ratio, average particle size 0.25μ) 300mg/refined gelatin 170 Compound-■
7 Dodecylbenzenesulfonate sodium salt dihexyl α-sulfosuccinate sodium salt Polystyrene sulfonate sodium salt formulation - ■ Back layer gelatin compound - ○ compound - ○ compound - ○ compound - ○ Dodecylbenzenesulfonate sodium salt dibenzyl-α-sulfosuccina -tosodium salt 1.2-bis(vinylsulfonylacetamide)ethaneethyl acrylate latix (average particle size 0.05μ) perfluorooctane sulfo lO■/resistance 9 〃 2, Ig/rrr ioo■/d 100" 100 ”! 0" 70 〃 15 〃 120" 5001 nonacid lithium salt 10 mg/m silicon dioxide fine powder particles (average particle size 4 μ, pore diameter 170, surface area 300 m/g) 35 〃Additionally,
The following coating was applied to the opposite side.

Compound-〇CH3CC-C)I CCCH- 1)1)1I+ 100mg/r+ for 5O3K SO, Compound-■ 100mg/r+ for 5O8K SO3? Compound - ■ 5O3K 5O3K] 00mg/
Resistance (preparation of emulsion) A mixed aqueous solution of potassium iodide and potassium bromide containing KalrCne and (NH4)IRh C1a and an aqueous solution of silver nitrate were mixed in 1. A gelatin aqueous solution containing 8-dihydroxy-3,6-cythiaoctane was stirred vigorously and heated to 52°C.
for 15 minutes 1) Add while controlling the Ag content to 7.7, containing 0.5 mol% silver iodide, and finally halogenating 31 rcj'a and (NH<)sRh C1a. Monodisperse cubic silver iodobromide with an average grain size of 0.21 microns was obtained, each containing 10-' moles per mole of silver. Using this silver iodobromide emulsion as a core, under the same precipitation environment as the first precipitation, a potassium bromide aqueous solution and a silver nitrate aqueous solution were added while controlling the pAg of the solution to 7.4, and the average particle size was A monodisperse cubic core/shell silver iodobromide emulsion (average silver iodide content 0.5 mol %) with a diameter of 0.28 μm was obtained. After washing with water and desalting, 3 mg of sodium thiosulfate and 4 mg of chloroauric acid were added to this emulsion per mole of silver, heated at 65°C for 70 minutes, and chemically sensitized. 30 mg of a 1% solution of 6methyl-1.3.3a,7-chitrasaindene was added.

Using this emulsion, 3-ethyl-2[3-ethylbenzothiazolinylidene-methylidene]-5-C3-ethyl-4methyl-thiazolinylidene-ethylidene)-loader was added as a spectral sensitizing dye. Niniodine salt and 4.4'-
Bis(dinaphthoxy-pyrimidylamino))stilbene-2,2-disulfonic acid disodium salt was added at 20 μm per mole of silver halide, and l-phenyl-5-mercaptotetrazole was added as an antifoggant at 1 mole of silver. 50 μm per mole, polyethyl acrylate latex as a plasticizer at a ratio of 25% to the seratin binder, 2-bis(vinylsulfonylacetamido)ethane as a hardening agent 1)0μ/v, and silver 3.5% per mole were added. 2g/
It was applied so that it became m. Gelatin was 1.8 g/rrr.

On top of this, 0.9 g/m of gelatin is used as a protective layer, and 60 μm of polymethyl methacrylate with a particle size of 3 to 4 μm is used as a matting agent.
/M, Hydroquinone 150■/, as an antifoggant
(Sample 3-0 was obtained by simultaneously coating a layer containing dodecylbenzenesulfonic acid sodium salt and a fluorine surfactant having the following structural formula @ as a coating aid.

@C,F,7SC)2NCH2COOKC,H.

Compound IV-1 was added to the protective layer of sample 3-0 above in an amount of 180 μ/bo. Sample 3-1.2. was prepared in the same manner as 3-0 except that in addition to this, the amount of gelatin in the protective layer was adjusted to 0.9 g/rrr.
I got 3.

The sample thus obtained was wedge-exposed with a He-Ne laser beam having an emission maximum at 633 nm, and was exposed using Fuji Photo Film Co., Ltd.'s developer LD-745 and LF as a fixer.
-308 (manufactured by Fuji Photo Film Co., Ltd.) at 38°C with processor FG71ONH manufactured by Fuji Film Co., Ltd.
It was developed for tO seconds, fixed, washed with water, and dried. The development processing time from when the leading edge of the photographic light-sensitive material was immersed in the developer to when the leading edge came out of the final drying zone was 30 seconds.

Note that safelight safety and residual color evaluation were determined as follows.

1) Safelight safety: After being left for 3 minutes at a distance of 1 m under the green Safelight (Fuji Safelight Filter Nα4) of a 20W light bulb, the film was developed and the increase in fog density was measured.

2) Remaining color property 2 Samples were prepared by developing, fixing, washing and drying using the method described above, and the color tone of the unexposed areas was visually evaluated. r5J represents the best quality and rlJ represents the worst quality.

Table 5 shows the evaluation results for samples 3-0, 1, and 2.3. As is clear from Table 5, it can be seen that when the dispersion of the present invention is used, a photographic material with excellent safelight safety and no residual color can be obtained.

Table 5 protective layer dye The decolorizing solubility is fast even when the color is removed, and residual color is not a problem.

Further, the sharpness can be improved by reducing the amount of dye applied, or by keeping the amount of dye applied the same.

In addition, when used as a filter layer, it was confirmed that significant effects such as improved coating surface condition, good safelight safety, and improved decolorization properties were obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. (Effects of the Invention) According to the present invention, when used in an antihalation layer, it can be dyed sufficiently selectively, without reducing the sensitivity of other layers, and there is significantly less residual color. Become.

Particularly in the case of rapid processing where the development processing time is 45 seconds or less Relationship with cases involving persons who correct silver halide photographic light-sensitive materials

Claims (3)

[Claims] (1) A silver halide photographic material having at least one hydrophilic colloid layer containing a solid-dispersed dye,
A halogenated dye, characterized in that the average particle diameter of the dye is within the range of 0.1 μm to 0.6 μm, and the coefficient of variation (as defined in the specification) of the particle size distribution is 50% or less. Silver photographic material. (2) The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is used for a developing time of 45 seconds or less. (3) The silver halide photographic light-sensitive material was developed for 3
The silver halide photographic material according to claim 1, wherein the silver halide photographic material is used for 0 seconds or less.