JP2549929B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inert and is easily decolorized in the course of photographic processing. And / or a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a dye to be eluted.

(Prior Art) In a silver halide photographic light-sensitive material, a photographic emulsion layer 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 to be incident on the photographic emulsion layer, a coloring layer is provided on the side of the photographic light-sensitive material 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 a multilayer color light-sensitive material, a filter layer may be located between them.

Based on the fact that the 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 re-enters the photographic emulsion layer. For the purpose of preventing image blurring, that is, halation, a coloring layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. When a multilayer color is a light-sensitive material, an antihalation layer may be provided between the layers.

Further, in the X-ray sensitive material, a colored layer for improving sharpness may be provided as a crossover cut filter for reducing crossover light.

Decrease in image sharpness due to scattering in photographic emulsion layer (this decrease is commonly called irradiation)
Coloring of the photographic emulsion layer is also carried out in order to prevent the above phenomenon.

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

(1) It has a proper spectral absorption according to the purpose of use.

(2) Photochemically inactive. That is, the performance of the silver halide photographic emulsion layer must not be adversely affected in a chemical sense, for example, decrease in sensitivity, regression of a latent image, or fogging.

(3) It is decolorized in the course of photographic processing, but is not dissolved and removed to leave a harmful direct color on the photographic light-sensitive material after processing.

Greater efforts have been made by those skilled in the art to find dyes that meet these conditions, and the following dyes are known. For example, British Patent Nos. 506,385 and 1,177,429,
1,311,884, 1,338,799, 1,385,371, 1,4
Nos. 67,214, 1,433,102, 1,553,516, JP-A-48-
85, 130, 49, 114, 420, 50-147, 712, 55-1
61,233, 58-143,342, 59-38,742, 59-1
11,641, 59-111,640, U.S. Pat.No. 3,247,127,
Oxonol dyes having a pyrazolone nucleus and a barbituric acid nucleus described in 3,469,985 and 4,078,933 etc., U.S. Pat.Nos. 2,533,472, 3,379,533, and British Patent 1,27.
Other oxonol dyes described in 8,621, British Patents 575,691, 680,631, 599,623, 786,9
07, 907,125, 045,609 U.S. Pat.No. 4,255,326
Azo dyes described in JP-A-59-211,043, JP-A-50-100,116, JP-A-54-118,247, and British Patent No. 2,01.
Azomethine dyes described in 4,598, 750,031 and the like,
Anthraquinone dyes described in U.S. Patent No. 2,865,752, U.S. Patent Nos. 2,538,009, 2,688,541, 2,538,
008, British Patents 584,609, 1,210,252, JP-A-5
0-40,625, 51-3,623, 51-10,927, 54-
118,247, Japanese Examined Patent Publication Nos. 48-3,286, 59-37,303, etc., arylidene dyes, Japanese Examined Patent Publication Nos. 28-3,082, 44
-16,594, 59-28,898 and the like styryl dyes, British Patent Nos. 446,583, 1,335,422, JP-A-59-
Triarylmethane dyes described in No. 228,250, British Patent Nos. 1,075,653, 1,153,341 and 1,284,730
No. 1,475,228, No. 1,542,807 and the like, and merocyanine dyes described in US Pat. Nos. 2,843,486 and 3,294,539.

Among these, the arylidene dyes having a pyrazolone nucleus and the oxonol dyes having two pyrazolone nuclei have the property of being decolorized in a developer containing a phosphite salt, and are useful dyes having little adverse effect on a photographic emulsion. Has been used as a dye in photosensitive materials.

However, among the dyes belonging to this system, even if it has little effect on the photographic emulsion itself, spectrally sensitized emulsions can be spectrally sensitized to unnecessary areas or desensitized dyes can be desorbed. This has the drawback of causing a decrease in sensitivity that is thought to be due to the above.

In addition, there are some that remain after the processing due to the speeding up of the developing processing that has recently been performed. In order to solve this, it has been proposed to use a dye having a high reactivity with sulfite ion, but in this case, the stability in the photographic film is not sufficient, and the density decreases with time, It has the drawback that the desired photographic effect cannot be obtained.

On the other hand, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. Is usually required. This is because otherwise, not only the effect as a filter layer or an antihalation layer is deteriorated but also a harmful spectral action is exerted on other layers. There are several methods for selective coloring of a specific hydrophilic colloid layer. However, a hydrophilic polymer containing a portion having an opposite charge to a dye ion coexists as a mordant in the hydrophilic colloid layer. The most commonly used method is to localize the dye in a specific layer by interaction with the dye molecule, which is believed to be attraction and hydrophobic binding due to charge.

However, when the mordant method is used, when the layer to which the dye is added and the other hydrocolloid layer are in contact with each other in a wet state, a part of the dye often diffuses from the former to the latter. Such diffusion of the dye depends, of course, on the chemical structure of the mordant, but also on the chemical structure of the dye used.

Further, when a polymer mordant is used, residual coloring is particularly likely to occur on the light-sensitive material after photographic processing, particularly photographic processing with a shortened processing time. This is because the binding force of the mordant to the dye is considerably weakened in an alkaline liquid such as a developing solution, but since some binding force still remains, the dye or the reversible decolorization product remains in the layer containing the mordant. It is thought to be because it does.

Further, as another means for keeping a dye in a specific layer in a photographic light-sensitive material, JP-A-56-12639, JP-A-55-155350 and JP-A-55-1
55351, 52-92716, 63-197943, 63-2783
No. 8, No. 64-40827, European Patent 0015601B1, No. 0
It has been proposed to have the dye present as a dispersed solid as disclosed in 276566A1, WO 88/04794.

However, if the dye is made into a dispersed solid state, the international application publication
As described in No. 88/04794, the absorption spectrum of the dispersed solid coating has a shift in absorption peak as compared with the absorption spectrum of a solution of the same dye or the absorption spectrum of a dye dissociated at pH 10, and a half value width ( It is clear that the spread of HBW) is a characteristic.

Coloring of the full width at half maximum is suitable for filter applications that require exposure in a wide wavelength range. But,
According to the research conducted by the present inventor, it has a drawback that the absorbance value is generally small. Further, in the multilayer silver halide material, it is rather disadvantageous that the full width at half maximum is too wide for applications such as a filter for blocking light of unnecessary wavelength in the spectral sensitivity region of the lower layer, such as a yellow filter or a magenta filter. Is. In addition, when used for the antihalation layer of the photosensitive layer whose spectral sensitivity region is in a very narrow wavelength region, or when used for an antihalation layer when exposed to light in a very narrow wavelength region, the absorbance is That is, a large amount of dye coating is required, which results in many disadvantages such as decolorization deterioration, thick film thickness, and cost increase.

(Problems to be Solved by the Invention) Therefore, the object of the present invention is, firstly, that the hydrophilic colloid layer is colored with a dye which is irreversibly decolorized by photographic processing and which does not adversely affect the photographic characteristics of the photographic emulsion. Another object of the present invention is to provide a silver halide photographic light-sensitive material.

Secondly, the object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer in which only a desired hydrophilic colloid layer is sufficiently selectively dyed with a dye and which is excellent in decolorization by photographic processing. That is.

Thirdly, an object of the present invention is to provide a novel method for immobilizing a dye, which has a high absorbance and a sharp absorption.

(Means for Solving the Problem) As a result of intensive investigations by the present inventors, the dye represented by the general formula [I] or [II] has a high absorbance and a high absorption by the method as described below. It was found that a solid dispersion having a sharp absorption spectrum with a full width at half maximum of 90 nm or less was obtained, and it was clarified that the above object was achieved by this.

Considering the general knowledge that the absorption spectrum of the dispersed solid gives a broad absorption spectrum as described above, it was not expected that such a sharp dispersed solid dye would be obtained. It's a term.

General formula (I) In the formula, R ₁₁ represents an aryl group or an aralkyl group having at least one carboxylic acid group, and R ₁₂ represents an alkyl group, an aryl group, an aralkyl group, a cyano group, —COOR ₁₇ ,
-CONR ₁₇ R ₁₈ , -COR ₁₉ , -SO ₂ R ₁₉ , -SOR ₁₉ , -SO ₂ NR ₁₇
R ₁₈ , -OR ₁₇ , -NR ₁₇ R ₁₈ , -NR ₁₈ COR ₁₉ , -NR ₁₇ CONR ₁₇ R
₁₈ or -NR ₁₈ SO ₂ R ₁₉ (wherein R ₁₇ , R ₁₈ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁₉
Represents an alkyl group, an aralkyl group or an aryl group,
R ₁₇ and R ₁₈ or R ₁₈ and R ₁₉ may combine to form a 5- or 6-membered ring. ) Represents, R _13, R ₁₄ is a hydrogen atom, a halogen atom, an alkyl group, an aryl _{group, -OR 17, -NR 17 R 18} , -
NR ₁₈ COR ₁₉ , −COOR ₁₇ , −CONR ₁₇ R ₁₈ (where R ₁₇ ,
R ₁₈ and R ₁₉ have the same meaning as R ₁₇ , R ₁₈ and R ₁₉ defined above. And R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, and R ₁₅ and R ₁₆ are linked to each other to form 5 or 6
A member ring may be formed, or R ₁₃ and R ₁₅ or R ₁₄ and R ₁₆ may be connected to each other to form a 5- or 6-membered ring.

L ₁₁ , L ₁₂ and L ₁₃ each represent a methine group, and n represents 0 or 1.

General formula (II) In the formula, R ₂₁ and R ₂₃ each have the same meaning as R ₁₁ in formula (I), and R ₂₂ and R ₂₄ each have the same meaning as R ₁₂ in formula (I). L ₂₁ , L ₂₂ and L ₂₃ each represent a methine group,
m represents 0, 1 or 2.

 The general formula (I) will be described in detail.

An aryl group or an aralkyl group having at least one carboxylic acid group represented by R ₁₁ is a substituent other than a carboxylic acid group [eg, an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy), halogen Atoms (eg chlorine, bromine, fluorine), amino groups (eg dimethylamino, diethylamino), hydroxyl groups, cyano groups,
A phenoxy group]. The aryl group represented by R ₁₁ has 6 to 12 carbon atoms, and is preferably a phenyl group or a naphthyl group, and specific examples include 4-
Carboxyphenyl, 2,5-dicarboxyphenyl, 2
-Methyl-4-carboxyphenyl, 2,4-dicarboxyphenyl, 2-carboxyphenyl, 3-carboxyphenyl, 2-methoxy-4-carboxyphenyl, 2-
Hydroxy-4-carboxyphenyl, 3,5-dicarboxyphenyl, 3,6-dicarboxy-2-naphthyl 6,8-
Examples include groups such as dicarboxy-2-naphthyl.

The aralkyl group having at least one carboxylic acid group represented by R ₁₁ has from 7 to 15 carbon atoms, and preferably represents a benzyl group or a phenethyl group, specifically 2
-Carboxybenzyl, 4-carboxybenzyl, 2,4
-Dicarboxybenzyl, 4-carboxyphenethyl,
Groups such as 2-methyl-4-carboxybenzyl and the like can be mentioned.

The alkyl group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ is an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl). , Isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, n-hexyl, n-octyl, isoamyl) are preferable, and substituents (for example, halogen atom such as fluorine, chlorine, bromine, phenyl group, hydroxyl group, cyano) Groups, alkoxy groups (eg methoxy, ethoxy, hydroxyethoxy),
Aryloxy group (eg, phenoxy, p-methoxyphenoxy), carboxy group, amino group, substituted amino group (eg, dimethylamino, diethylamino), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, i-propoxycarbonyl), carbamoyl group ( For example, methylcarbamoyl, ethylcarbamoyl, 2-hydroxyethylcarbamoyl), sulfamoyl group (eg methylsulfamoyl) acylamino group (eg acetylamino, propanoylamino), sulfonamide group (eg methanesulfonamide, ethanesulfonamide)] You may have.

The aryl group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ has 6 to 12 carbon atoms, and specific examples include a phenyl group, A naphthyl group is preferable, and a substituent [for example, a halogen atom such as fluorine, chlorine, or bromine, a carboxy group, a hydroxyl group, a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl), an alkoxy group ( For example, methoxy, ethoxy), an aryloxy group (eg, phenoxy)] may be included.

The alkyl group represented by R ₁₂ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ is an aralkyl group having 7 to 15 carbon atoms (eg, benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl). , 4-phenylbutyl, naphthylmethyl) are preferred, and substituents [for example, a halogen atom such as fluorine and chlorine, a hydroxyl group, a cyano group, an alkoxy group (for example, methoxy, ethoxy), a carboxy group, an amino group, a substituted amino group, (for example, Dimethylamino, diethylamino), an alkoxycarbonyl group (for example, ethoxycarbonyl)].

Examples of the 5- or 6-membered ring formed by linking R ₁₇ and R ₁₈ or R ₁₅ and R ₁₆ include a piperidine ring, a morpholine ring, and a pyrrolidine ring, and R ₁₈ and R ₁₉ are linked. Examples of the 5- or 6-membered ring formed include a pyrrolidone ring and a piperidinone ring.

The alkenyl group represented by R ₁₅ and R ₁₆ has 3 to 6 carbon atoms.
The alkenyl group of is preferably an allyl group, 3-
A group such as a hexenyl group can be mentioned.

The acyl group represented by R ₁₅ and R ₁₆ is preferably an acyl group having 2 to 8 carbon atoms, and specific examples thereof include acetyl, propionyl, pivaloyl, hexanoyl, benzoyl and 2-methylpropionyl.

A sulfonyl group represented by R _15, R ₁₆ is preferably a sulfonyl group having 1 to carbon atoms, specifically methanesulfonyl, ethanesulfonyl, butanesulfonyl, benzenesulfonyl, and the groups such as p- Torr Hong sulfonyl it can.

The methine group represented by L ₁₁ , L ₁₂ and L ₁₃ may have a substituent (eg, methyl, ethyl, cyano, phenyl, chlorine atom).

In the above general formula (I), the carboxylic acid group represents a free acid form.

Specific examples of the dye represented by formula (I) used in the present invention are listed below.

The synthesis of the dye represented by formula (I) is described in JP-A-51-
No. 3623, No. 48-68623, No. 52-20822, No. 56-12639
No. 59-154439, No. 59-211,041, No. 60-135937.
No. 62-106455, No. 62-133453, No. 63-197943, etc., or can be easily carried out by condensation of pyrazolones and benzaldehydes according to the described method. .

 Next, general formula (II) will be described.

The methine group represented by L ₂₁ , L ₂₂ , and L ₂₃ is a substituent [for example, an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, 2-hydroxyethyl), an aryl group (for example,
Phenyl, 4-chlorophenyl), a halogen atom (eg, F, Cl, Br, I), a substituted amino group (eg, dimethylamino, anilino)], and the substituents are 5- or 6-membered rings. [For example, (Here, R ₂₅ and R ₂₆ are each an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl) or a 5- or 6-membered ring formed by linking R ₂₅ and R ₂₆ (eg, pyrrolidine). Ring, piperidine ring, morpholine ring).] Specific examples of the dye represented by formula (II) used in the present invention are listed below.

The dye represented by the general formula (II) is represented by JP-B-43-3504.
No. 48-85130, No. 52-92716, No. 54-147712
No. 60-218641, No. 63-244034, No. 64-40827, or can be synthesized according to the method described.

A solid dispersion of a dye having such absorption properties can be obtained by carefully mixing an acid with an alkaline aqueous solution of the dye in the presence of gelatin.

The method of precipitating a dye by adjusting the pH from a solution of the dye to obtain a dispersed solid is itself suggested in the above-mentioned International Application Publication No. 88/04794, but a ball mill, a sand mill, a colloid mill, etc. There is only a description in parallel with the method of making a mechanically dispersed solid according to the present invention, but there is no example, let alone a mechanical dispersing method and a method of dispersing by adjusting pH as shown in the examples of the present invention. It does not give any suggestion that there may be such a remarkable difference, and it can be said that it is unexpected. Similarly, JP-A-52-92
As a general description in No. 716, a method of obtaining a dispersed solid at the time of application by applying a dissociated dye in the form of a salt and then overcoating with acidic gelatin is disclosed. There is no data suggesting such a remarkable feature.

It is not clear whether the absorption characteristics differ in this way regardless of the water-insoluble dye solid in the same non-dissociated state, but the crystal form is different depending on the precipitation method, or the particle size distribution It is presumed to be due to the difference.

The dispersed solid of the compound of the general formula [I] or [II] is used in an amount of 1-1000 mg / m ² on the light-sensitive material, preferably 1-800 mg / m ² .

When a dispersed solid of a compound of the general formula [I] or [II] is used as a filter dye or an antihalation dye, an effective and cautious amount can be used, but the optical density is
It is preferable to use it in the range of 0.05 to 3.5. The timing of addition may be any step before coating.

The dispersed solid of the compound of the general formula [I] or [II] according to the present invention can be used in any of the emulsion layer and other hydrophilic colloid layers.

The solid dispersion of the compound represented by the general formula [I] or [II] of the present invention is obtained as an alkaline aqueous solution by adjusting the pH at which the dye is dissolved, and then as a fine solid precipitate by lowering the pH. The solution is prepared in the presence of a protective colloid such as gelatin. The solid dispersion can be prepared not only by the presence of gelatin etc., but also by a surfactant, a silver halide emulsion or emulsion or a polymer latex, or a compound necessary for the preparation of other silver halide photographic light-sensitive materials. Can be prepared in the coexistence of

In this way, a dispersed solid is obtained which gives a sharp absorption spectrum with a half-value width of 90 nm or less when the transmission absorption spectrum of the coating film at 350 nm to 850 nm is measured.

The dye of the present invention in the dispersion has an average particle size of 10 μm or less,
It is more preferably 2 μm or less, and particularly preferably 0.5.
μm or less.

As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids usable for photography can be used.

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

The silver halide grains used in the present invention have a regular crystal form such as a cube and an octahedron, and an irregular shape such as a sphere and a plate.
Those having different crystal forms, or those having a composite form of these crystal forms. It is also possible to use a mixture of grains having various crystal forms, but it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Also, grains in which a latent image is mainly formed on the surface (eg, negative emulsion) may be used, and grains in which the latent image is mainly formed (eg, internal latent image type emulsion, pre-fogged direct reversal type emulsion) May be Preferably, the particles are such that the latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5.
Micron or less, preferably 0.3 micron or less, diameter is preferably 0.6 micron or more, and average aspect ratio is 5
A tabular grain emulsion in which the above grains occupy 50% or more of the total projected area, or a statistical coefficient of variation (in the distribution represented by a direct system when the projected area is approximated by a circle, the standard deviation S is divided by the diameter. Monodisperse emulsions with a value S /) of less than 20% are preferred. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is Chimie er Physique Photographeque by P. Glafkides.
(Published by Paul Montell, 1967), GFDuffin, Photographic Emulsion Chemistr
y) (Focal Press, 1966), VLZelikman et al., Making and
Coating / Photographic, Emulsion (Ma
king and Coating Photograhic Emulsion) (published by Focal Press, 1964) and the like.

Further, in order to control the growth of grains during the formation of the silver halide grains, as materials for silver halide, for example, ammonia, rodancali, rodanmon, thioether compounds (e.g., U.S. Pat.Nos. 3,271,157 and 3,574,6
No. 28, No. 3,704,130, No. 4,297,439, No. 4,276,
374) and thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, etc.) and amine compounds (for example, JP-A No. 54-100717).

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 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,
Various synthetic hydrophilic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used.

In addition to general-purpose coal-processed gelatin, acid-processed gelatin and the Japan Society for Science and Photography (Bull.Soc.Sci.Pho.
t. Japan), No. 16, p. 30, page 1966 (1966), or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer may contain an inorganic or organic hardener. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-
Triazine and its sodium salt, etc. and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or vinylsulfonyl groups as side chains Is preferred since a hydrophilic colloid such as gelatin can be rapidly cured to provide stable photographic characteristics. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3
-Pyridinio) methanesulfonate) and haloamidinium salts (1- (1-chloro-1-polydinomethylene) pyrrolidinium 2-naphthalene sulfonate etc.) have a fast curing rate and are excellent.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and 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 normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus, etc .; a nucleus 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, an ionic renin nucleus, a benzindolenine nucleus, an indole nucleus, Benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohyditein nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for the purpose of color sensitization. Along with the sensitizing dye, a dye having no self-spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721) and an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,510) Described in), cadmium salt,
An azaindene compound or the like may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,635,7
The combination described in No. 21 is particularly useful.

The silver halide photographic emulsion used in the present technology should contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promotensimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; quercaptotriazine pairs; for example oxadrine Thioketo compounds such as thiones; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3
a, 7) Tetraasianindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. You can

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). But it's okay.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used.In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . The oil-soluble dye may 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, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as required. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive, blue-sensitive layer, green-sensitive and red-sensitive layers or blue-sensitive, red-sensitive and green-sensitive. Further, an arbitrary emulsion layer having the same color sensitivity may be composed of two or more different emulsion layers to improve the ultimate sensitivity, or a three-layer structure to further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having different color sensitivity may be inserted between certain emulsion layers having the same color sensitivity. A reflective layer of fine silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity.

It is common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases. For example, a combination of infrared-sensitive layers may be used for pseudo color image transfer or semiconductor laser exposure.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are a flexible support or glass such as plastic film, paper, cloth and the like which are usually used for photographic light-sensitive materials, glass, ceramics,
It is applied to a rigid support such as metal. Useful as flexible supports are cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
It is a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate or polycarbonate, a baryta layer or a paper coated or laminated with an α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer) or the like. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. U.S. Pat.No. 2,681,294 as required,
Multilayers may be simultaneously coated by the coating method described in Nos. 2761791, 3526528, 3508947 and the like.

The present invention can be applied to various color and black and white light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials. it can. Further, a direct positive color using an internal latent image type silver halide emulsion which has not been fogged and is described in JP-A-63-159847 can also be applied to a light-sensitive material. By utilizing the tri-color coupler mix described in Research Disclosure, No. 17123 (July 1978), or by utilizing the black color couplers described in US Pat. No. 4,126,461 and British Patent No. 2,102,136. As a result, the present invention can be applied to a black-and-white light-sensitive material for X-rays. Plate-making film such as squirrel film or scanner film, X-ray film for direct / indirect medical treatment or industrial use,
The present invention can be applied to negative black and white film for photography, black and white photographic paper, for COM or ordinary microfilm, silver salt diffusion transfer type photosensitive material and printout type photosensitive material.

Various exposing means can be used for the light-sensitive 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 light source or the writing light source. Flashlight sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. It emits light in the wavelength range from ultraviolet to infrared,
A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source can also be used as the recording light source. In addition, the fluorescent surface (CRT, etc.) emitted from the fluorescent substance excited by the electron beam, liquid crystal (LCD), or lanthanum-doped lead titan zirconate (PLZT) throat is used as a linear or micro-shutter array. An exposure means combining a planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

Examples of the developing agent used in the developer used when the light-sensitive material of the present invention is a black-and-white light-sensitive material include dihydroxybenzenes, 1-phenyl-3-pyrazolidones, p-aminophenols and the like.

Dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,
There are 3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, with hydroquinone being particularly preferred.

As p-aminophenol-based developing agents, N-methyl-p-aminophenol, p-aminophenol, N-
(Β-hydroxyethyl) -p-aminophenol, N
-(4-hydroxyphenyl) glycine, 2-methyl-
Although there are p-aminophenol, p-benzylaminophenol and the like, N-methyl-p-aminophenol is preferable among them.

1-phenyl- as a 3-pyrazolidone developing agent
3-pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4
-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Trily-4-methyl-4-hydroxymethyl-3-pyrazolidone, and the like.

The developing agent is preferably used in an amount of 0.001 mol / -1.2 mol /.

As preservatives, sodium sulfite, potassium sulfite,
Examples include lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. Sulfite
0.2 mol / or more Especially 0.4 mol / or more is preferable. The upper limit is preferably 2.5 mol / up.

 The pH of the developer is preferably in the range of 9 to 13.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, etc.
Contains pH regulator.

JP-A-62-186259 (borate), JP-A-60-93433
Buffers (eg, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

A hardener may be used in the developer. As the hardener, a dialdehyde hardener or a bisulfite adduct thereof is preferably used, and specific examples thereof include glutaraldehyde, or a bisulfite adduct thereof.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol Organic solvents such as: 1-phenyl-5-mercaptotetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, benz such as 5-methylbenztriazole Anti-foggants such as triazole compounds may be included in Research Disclos
ure Vol. 176, No. 17643, page XXI (December issue, 1978), development accelerators, and if necessary, toning agents, surfactants, defoaming agents, water softeners, JP-A It may contain an amino compound described in JP-A-56-106244.

The fixer is an aqueous solution containing thiosulfate as a fixer and has a pH of 3.8 or higher, preferably 4.2 to 7.0. More preferably, the pH is 4.5 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to 6 mol / mol.

The fixer may also contain water-soluble aluminum salts which act as hardeners, such as aluminum chloride, aluminum sulphate, potassium alum.

Tartaric acid, citric acid, gluconic acid or their derivatives may be used alone or in combination of two or more in the fixing solution. These compounds are 0.00 per fixing solution
Those containing more than 5 moles are effective, especially 0.01 mole / ~ 0.03
Molar / is particularly effective.

Preservatives (eg, sulfite, bisulfite), pH buffering agents (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having water softening ability, and JP-A The compounds described in 62-78551 may be included.

When the light-sensitive material of the present invention is a color light-sensitive material, the color developing solution used in the development processing is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and its representative example is 3-methyl-4.
-Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Examples thereof include amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

The color developing solution is a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. It typically includes a throat. If necessary, preservatives such as hydroxyamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dyes. Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids,
Various chelating agents typified by aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, and antioxidants described in West German Patent Application (OLS) No. 2,622,950 may be added to the color developer.

In the development processing of a reversal color light-sensitive material, black and white development is usually performed before color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N.
Known black-and-white developing agents such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Examples of bleaching agents include iron (III), cobalt (III), chromium (I
Compounds of polyvalent metals such as V) and copper (II), peracids, quinones, nitrones and the like are used. Representative bleaching agents are ferricyanides; dichromates; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid. Aminopolycarboxylic acids such as or citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates; manganates; nitrosophenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in a stand-alone bleaching solution as well as in a one-bath bleach-fixing solution.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
No. 988, JP-A Nos. 53-32736, 53-57831, and 37418.
No. 53, No. 53-65732, No. 53-72623, No. 53-95630,
53-59631, 53-104232, 53-124424, 5
Compounds having a mercapto group or a disulfide group described in 3-141623, 53-28426, Research Disclosure No. 17129 (July 1978), etc .;
Thiazolidine derivatives as described in 140129; JP-B-45-8506, JP-A-52-20832, JP-A-53-32735,
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715 and iodides described in JP-A-58-16235; Polyethylene oxides described in West German Patents 966,410 and 2,748,430; JP-B-45 Polyamine compounds described in JP-A No. 8836/8836;
And the compounds described in JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940 can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858 and West German Patent 1,290,812.
And the compounds described in JP-A-53-95630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable.
These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds thioureas, and a large amount of iodides, and thiosulfates are generally used. As the bleach-fixing solution and the preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After bleach-fixing treatment or fixing treatment, washing treatment and stabilizing treatment are usually carried out. Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation,
Water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae and mold, magnesium salts and aluminum salts bismuth salts If necessary, a metal salt typified by 1), a surfactant for preventing a drying load or unevenness, and various hardeners can be added. Or by West Photographic Sanence and Engineering magazine (LEWest, Pho
t.Sci.Eng.), Vol. 6, pages 344-359 (1965) and the like. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Further, instead of the water washing step, Japanese Patent Laid-Open No.
A multi-stage countercurrent stabilization treatment step as described in No. 8543 may be carried out. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water) for adjusting the membrane pH (eg pH 3 to 9). , A monocarboxylic acid, a dicarboxylic acid, a polycarboxylic acid and the like are used in combination) and an aldehyde such as formalin. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (bayazoisothiazolinone, irithiazolone, 4 -Thiazolin benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners and other various additives may be used, and the same or different target compounds may be used. You may use 2 or more types together.

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium nitrate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). On this occasion,
If the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be removed.

The washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, although it varies depending on the type of the photosensitive material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Indoaniline compounds described in No. 7, No. 3,342,599,
Research Disclosure No. 14850 and Schiff base type compounds described in No. 15159, aldol compounds described in No. 13924, metal salt complexes described in US Patent No. 3,719,492,
Starting with the urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133 and JP-A-56-59232
No. 56-67842, No. 56-83734, No. 56-83735,
56-83736, 56-89735, 56-81837, 56
-54430, 56-106241, 56-10723, 57-97
Examples thereof include various salt type precursors described in No. 631 and No. 57-83565.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339, JP-A-57-144547, and JP-A-57-21114.
No. 7, No. 58-50532, No. 58-50536, No. 58-50533,
58-50534, 58-50535 and 58-115438.

The 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 it is possible to raise the temperature to accelerate the treatment and shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

In the case of continuous processing, a certain finish can be obtained by using a replenisher for each processing liquid to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

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

 Next, the present invention will be specifically described based on Examples.

Example 1 The following dye was dispersed as a solid by the following methods (1) to (5), and 0.07 g / m ^{2 of} the following solid was dispersed as a dye on the undercoated 180 μm polyethylene terephthalate transparent support.
A film coated with 3 g / m ^{2 of} gelatin and 0.06 g / m ² of 1,2-bis (vinylsulfonylacetamido) ethane as a hardening agent was prepared.

(1) The method described in Examples of International Application Publication No. 88/04764.
That is, 21.7 ml of water and Triton X-200 Surfactant (TX-2
00 ) (Rohm & Haas) 6.7% solution 2.65 g and 60 ml
Placed in a screw pig bottle. Add 1.0 g of dye to this solution
Was. 40 ml of zirconium oxide (ZrO) beads (2 mm diameter)
Add the lid tightly and place it in a mill and disperse for 4 days.
After that, mix with 12.5% gelatin aqueous solution to remove bubbles,
The beads were removed by rocking to obtain a dispersion.

(2) 72 g of 10% aqueous gelatin solution, 108 ml of water, Triton X-
200 ml of 6.7% solution of surfactant and 0.5 ml of 1N citric acid aqueous solution are added and stirred at 40 ° C, while 7 ml of 1N citric acid is fed from one tube and 7 g of dye is fed from the other tube. 100 ml of 1N sodium carbonate aqueous solution
5 ml of the dye solution dissolved in was simultaneously added at a speed of 5 ml / min to obtain a solid dispersion of the dye.

(3) 72 g of 10% aqueous gelatin solution, 108 ml of water, Triton X-
While adding 1.5 ml of 6.7% solution of 200 surfactant and 7.5 ml of 1N aqueous citric acid solution and stirring at 40 ° C, add 5 ml of the same dye solution as in (2) at a speed of 5 ml per minute from the tube. A solid dispersion of the dye was obtained.

(4) 72 g of 10% gelatin aqueous solution, 108 ml of water, Triton X-
200 ml of a 6.7% solution of surfactant and 5 ml of the same dye solution as in (2) were added and stirred at 40 ° C while 7.5 ml of 1N citric acid aqueous solution was added to the solid dispersion of the dye at a speed of 5 ml per minute. Got

(5) 72 g of 10% aqueous gelatin solution, 108 ml of water, Triton X-
200 ml of 6.7% solution of surfactant and 50 ml of the same dye solution as in (2) were added, and while stirring at 40 ° C, 55 ml of 1N citric acid aqueous solution was added at a speed of 2 ml per minute to prepare the dye. A solid dispersion was obtained.

Mastersizer the volume average particle size of each dispersed solid
Measured with Mastersizer (Malvern Instruments Ltd.) and the spectral absorption spectrum of the film coated on transparent polyethylene terephthalate undercoated with gelatin (measured with Hitachi 320 type spectrophotometer), the maximum absorption wavelength,
The absorbance at the maximum absorption wavelength and the full width at half maximum are summarized in Table 1.

As can be seen from Table 1, depending on the dispersion method, the maximum absorption wavelength shifts, the luminous intensity increases remarkably, the full width at half maximum decreases, and the absorption becomes very sharp. Table 1 also counts that this effect does not necessarily depend on the influence of particle size, and it can be seen that this effect is unpredictable.

Example 2 A solid dispersion was prepared from the dyes shown in Table 2 by the methods (1) and (4) of Example 1, and a coated film was prepared in the same manner as in Example 1.

Then, the spectral absorption spectrum of each coated film was measured, and the maximum absorption wavelength, the absorbance at the maximum absorption wavelength, and the half-width value are summarized in Table 2.

Compared to the dispersion method (1) using a mill, for example, the dispersion method (4) also shifts the maximum absorption wavelength, the absorbance is large, and the half-value width is 90 nm or less, and a coated film with extremely sharp absorption characteristics is obtained. Was given.

Example 3 The coated films prepared in Examples 1 and 2 were immersed in a phosphate buffer of pH 5.0 for 1 minute, rinsed with running water for 10 seconds and dried, and the absorbance was measured. It is shown as a fixed ratio in% and shown in Table 3. It is desirable that the fixing rate is high in the neutral to weakly acidic region.

Solid dispersions with unique absorption properties of the present invention include:
It is clear from the table that a fixing rate equivalent to that of mechanical dispersions known in the past can be obtained.

Example 4 The coated films prepared in Examples 1 and 2 were dipped in a phosphate buffer having a pH of 10.0 at a rate of 10 g / sodium sulfite at a rate of 10 g / dipping for 45 seconds into an air-bubbling solution, and then the pH was adjusted to 5 10 seconds in phosphate buffer followed by running water for 10 seconds
After rinsing for 2 seconds and drying, the absorbance was measured. The ratio to the absorbance before the treatment was taken as the residual color ratio and expressed in%, and is also shown in Table 3. The condition in which sodium sulfite is present in the high pH region is generally closer to that of the developing solution, and therefore the lower residual color ratio is desirable.

As is clear from Table 3, the solid dispersion of the present invention is
It can be seen that the residual color ratio is equal to or higher than that of the dispersions obtained by the conventionally known mechanical method.

Example 5 Multi-layer color printing papers 5 to 5 having the following layer constitutions were prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-1) 8.2 g, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture of 0.88 μm average grain size and 0.70 μm average grain size (silver molar ratio). The variation coefficient of grain size distribution is 0.08 and 0.10, and each emulsion is silver bromide.
The following blue-sensitive sensitizing dyes were added to the large-sized emulsion at 2.0 × 10 ⁻⁴ mol per mol of silver, and 0.2 × 10 ⁻⁴ mol was added to the small-sized emulsion. , 2.5 × 10 ⁻⁴ mol of each was added, and then sulfur-sensitized. The emulsified dispersion of the previous period and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The coating solutions for the second layer to the seventh layer were prepared in the same manner as the coating solution for the first layer, and the added dye was added to the second layer in No.
The following was done according to. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye for each layer.

(Each mol of silver halide is 2.0 × 10 ^-4 mol for large size emulsion, and each is for small size emulsion.
2.5 × 10 ^-4 mol) (4.0 × 10 ^-4 mol for each large-sized emulsion and 5.6 × 10 ^-4 for each small-sized emulsion per mol of silver halide)
Mol) and (For large emulsions per mol of silver halide,
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mol) (For large emulsions per mol of silver halide,
0.9 × 10 ^-4 mol, or 1.1 × 10 ^-4 for small emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidoenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, per mol of silver halide.
5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol, and 2.5 × 10 ^-4 mol were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 mol, respectively, per mol of silver halide. ×
10 ⁻⁴ mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY ) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average particle size and 0.39 μm average particle size (Ag mol) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and AgBr0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv) -5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm and 0.45 µm in average grain size, Ag molar ratio) Variation in grain size distribution The coefficients are 0.09 and 0.11, AgBr0 for each emulsion.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.17 Liquid paraffin 0.03 Only the second layer is a multi-layer color photographic paper 5--dye I
It was prepared by adding a solid dispersion as shown in the table below so that only -2 was additionally applied and correcting the gelatin amount to be the same. The solid dispersion was prepared according to the dispersion methods (1) and (4) of Example 1 except that the dye was changed to I-2.

First, a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, color temperature of light source: 3200 ° K) was used for each sample, and gradation exposure of a three-color separation filter for sensitometry was performed. The exposure at this time was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds.

The exposed sample was processed using an automatic developing machine, using a solution having the following processing steps and processing solution composition.

Step Temperature Time Color developing 35 ° C. 45 seconds blix 30 to 35 ° C. 45 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 20 sec Drying 70 to 80 ° C. 60 seconds (to rinse → The above three tanks were of the countercurrent type.) The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N-N-tetramethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-Ethyl-N- (β-methane (Sulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g N, N-bis (carboxymethyl) hydrazine 5.5 g Optical brightener (WHITEX4B, Sumitomo Chemical Co., Ltd.) 1.0 g Water added 1000 ml pH (25 ° C) 10.05 Bleach-fixing solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Water 1000 ml pH (25 ℃ ) 6.0 Rinse solution Ion-exchanged water (calcium and magnesium are 3ppm or less for each) The processed sample is measured with the TCD type densitometer manufactured by Fuji Photo Film Co., Ltd. to measure the color density of blue, green and red light exposed areas, and the sensitivity is measured. Table 5 shows the relative sensitivity to the sample of 5 in which no dye was added.

Next, a sensitometer (manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K) was used for exposure through a green filter and an optical wedge for measuring sharpness. The exposure time was 1 second.

Table 5 shows the results of determining the sharpness of the treated samples in the same manner as the above treatment.

Sharpness is a quantity that represents the sharpness of the outline of an image and the ability to render a fine image. A value called CTF is used here. CTF represents the degree of attenuation of amplitude with respect to spatial frequency as a square waveform. In Table 5, spatial frequency 10 lines / m
The CTF (%) at m is shown. The larger the value, the higher the sharpness and the better.

As shown in Table 5, the dispersion of the present invention having a sharp absorption naturally has a lower green sensitivity than the case of using the broad dispersion according to the method (1) at the same dye coating amount, but has a high visual sensitivity. It can be seen that the effect of improving the sharpness in the green region is remarkable. It can be seen that when the reduction in green sensitivity is set to the same level and the effect of improving the sharpness is set to the same level, the dispersion of the present invention has a small decrease in blue sensitivity. The blue region has low luminosity, and even if the sharpness is high in the measurement, the effect is visually small, and the disadvantage of the reduced blue sensitivity is large. It can be seen that it is advantageous in designing photographic paper.

Further, it is shown that when the mechanical dispersion is added with the green sensitivity until it becomes equivalent to that of the present invention, the minimum density increases and the color cannot be completely decolorized.

Example 6 The solid dispersion of the dye of the present invention (5) in place of the yellow colloidal silver of the 11th layer of the following multilayer color light-sensitive material was prepared so that the coating amount of the dye was 0.06 g / m ^2. A color light-sensitive material was prepared.

(Support) A multi-layer color light-sensitive material having each of the following compositions was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ₂ of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. In the chemical structural formulas, those in the form of a salt conformed to the notation of Chemical Abstract.

1st layer (antihalation layer) Black colloidal silver… 0.15 Gelatin… 1.9 UV-1 (UV absorber)… 0.03 UV-2 (UV absorber)… 0.06 UV-3 (UV absorber)… 0.07 Solv-2 ( Solvent) 0.08 ExF-1 (cyan dye) ... 0.01 ExF-2 (cyan dye) ... 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) AgI 4 mol% Uniform sphere equivalent diameter 0.4μ Coefficient of sphere equivalent variation 37 %, Plate-shaped particles Diameter / thickness ratio 3.0 Coating silver amount ... 0.4 Gelatin ... 0.8 ExS-1 (sensitizing dye) ... 4.0 × 10 ^-4 ExS-2 (sensitizing dye) ... 0.1 × 10 ^-4 ExS-5 ( Sensitizing dye) 6.5 × 10 ^-4 ExS-7 (sensitizing dye) 6.5 × 10 ^-4 ExC-1 (cyan coupler) 0.17 ExC-2 (cyan coupler) 0.05 ExC-3 (magenta colored cyan coupler) ) ... 0.09 3rd layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core high ratio 2: 1 internal high AgI sphere equivalent diameter 0.65μ, variation of sphere equivalent diameter) Coefficient 25%, tabular grain, diameter / thickness ratio 2.0) coating silver amount ... 0.55 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, sphere-corresponding diameter 0.
4μ, variation coefficient of equivalent sphere diameter 37%, spherical particles, diameter / thickness ratio 3.0) Silver coating amount ... 0.1 Gelatin ... 1.0 ExS-1 (sensitizing dye) ... 5.0 × 10 ^-4 ExS-2 (sensitizing dye) ... 0.2 x 10 ^-4 ExS-5 (sensitizing dye) ... 8.2 x 10 ^-4 ExS-7 (sensitizing dye) ... 8.2 x 10 ^-4 ExC-1 (cyan coupler) ... 0.31 ExC-2 (cyan coupler) ... 0.01 ExC-3 (magenta color cyan dye coupler) ... 0.09 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core shell ratio 2: 1, equivalent spherical diameter 0.7) μ, coefficient of variation of equivalent spherical diameter 25%, plate-like particles, diameter / thickness ratio 2.5) Coating silver amount 0.9 Gelatin 0.8 ExS-1 (sensitizing dye) 6.4 × 10 ^-4 ExS-2 (sensitizing dye) ) ... 0.9 x 10 ^-4 ExS-5 (sensitizing dye) ... 10.4 x 10 ^-4 ExS-7 (sensitizing dye) ... 10.4 x 10 ^-4 ExC-1 (cyan coupler) ... 0.07 ExC-4 (cyan coupler) )… 0.08 Solv-1 (solvent)… 0.07 Solv 2 (solvent) ... 0.07 Solv-3 (solvent) ... 0.02 Cpd-7 (antifoggant) ... 4.6 × 10 ^-4 fifth layer (intermediate layer) Gelatin ... 0.6 UV-4 (ultraviolet absorber) ... 0.03 UV- 5 (ultraviolet absorber) ... 0.04 Cpd-1 (color mixing inhibitor) ... 0.1 polyethyl acrylate latex 0.08 Solv-1 (solvent) ... 0.05 6th layer (low-sensitivity green emulsion layer) Silver iodobromide emulsion AgI 4 Mol% uniform type. Equivalent sphere diameter 0.4μ,
Sphere equivalent diameter 0.7μ, coefficient of variation of sphere equivalent diameter 37%, plate-like particles,
Diameter / thickness ratio 2.0 Coating amount of silver 0.18 Gelatin 0.4 ExS-3 (sensitizing dye) 2 × 10 ^-4 ExS-4 (sensitizing dye) 7 × 10 ^-4 ExS-5 (sensitizing dye) 1 × 10 ^-4 ExM-5 (magenta coupler) 0.11 ExM-7 (yellow colored magenta coupler) 0.03 ExY-8 (DIR coupler) 0.01 Solv-1 (solvent) 0.09 Solv-4 (solvent) 0.01 7th Layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface high AgI type with core shell ratio 1: 1, sphere equivalent type, sphere equivalent diameter 0.5 μ, variation coefficient of sphere equivalent diameter 20%, Plate-shaped particles, diameter / thickness ratio 4.0) Silver coating amount ... 0.27 Gelatin ... 0.6 ExS-3 (sensitizing dye) ... 2 × 10 ^-4 ExS-4 (sensitizing dye) ... 7 × 10 ^-4 ExS-5 ( sensitizing ^{dye) ... 1 × 10 -4 ExM-} 5 ( magenta coupler) ... 0.17 ExM-7 (yellow colored magenta couplers) ... 0.04 ExY-8 (DIR couplers) ... 0.02 Solv-1 (solvent) ... 0.14 Solv- (Solvent) 0.02 8th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (8.7 mol% AgI, multilayer structure grains with a silver content ratio 3: 4: 2, AgI content from the inside 24 mol, 0 mol %, 3 mol%, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter / thickness ratio 1.6) Coating silver amount ... 0.7 Gelatin ... 0.8 ExS-4 (sensitizing dye) ... 5.2 × 10 ^-4 ExS-5 (sensitizing dye) ... 1 x 10 ^-4 ExS-8 (sensitizing dye) ... 0.3 x 10 ^-4 ExM-5 (magenta coupler) ... 0.1 ExM-6 (yellow colored magenta coupler) ... 0.03 ExY-8 (DIR coupler) ... 0.02 ExC-1 (cyan coupler) ... 0.02 ExC-4 (cyan coupler) ... 0.01 Solv-1 (solvent) ... 0.25 Solv-2 (solvent) ... 0.06 Solv-4 (solvent) ... 0.01 Cpd-7 (antifoggant) ... 1 x 10 ^-4 9th layer (intermediate layer) Gelatin ... 0.3 Cpd-1 (color mixing inhibitor) ... 0.04 Polyethyl acrylate latex ... 0.12 Solv -1 (Solvent) ... 0.02 10th layer (donor layer for multi-layer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core high ratio AgI type of internal high AgI type, equivalent spherical diameter of 0.7μ, sphere) Coefficient of variation of equivalent diameter 25%, tabular grains, diameter / thickness ratio 2.0) Coating amount of silver: 0.68 Silver iodobromide emulsion (AgI 4 mol%, variation coefficient of equivalent spherical type diameter 37%, tabular grains, diameter / Thickness ratio 3.0) Coating silver amount ... 0.19 Gelatin ... 1.0 ExS-3 (sensitizing dye) ... 6 × ^10-4 ExM-10 (DIR coupler) ... 0.19 Solv-1 (solvent) ... 0.20 Solv-3 ... 0.05 11 layers (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0.8 Cpd-2 (yellow dye) 0.13 Solv-1 (solvent) 0.13 Cpd-1 (color mixing inhibitor) 0.07 Cpd-6 (antifoggant) 0.002 H-1 (hardener) 0.13 12th layer (low sensitivity blue sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent spherical diameter)
0.7μ, sphere equivalent diameter variation coefficient 15%, plate-like grains, diameter / thickness ratio 7.0) Silver coating amount: 0.5 silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 3.
0μ, coefficient of variation of equivalent spherical diameter 30%, plate-like particles, diameter / thickness ratio 7.0) Coating silver amount ... 0.25 gelatin ... 1.8 ExS-6 (sensitizing dye) 9 × 10 ^-4 ExC-1 (shican coupler) ... 0.06 ExC-4 (Sican coupler) ... 0.03 ExY-9 (DIR coupler) ... 0.14 ExY-11 (Yellow coupler) ... 0.89 Solv-1 (solvent) ... 0.42 13th layer (intermediate layer) Gelatin 0.7 ExY-12 (DIR Coupler) 0.20 Solv-1 (solvent) 0.34 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, coefficient of variation of sphere equivalent diameter 25%, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Amount of coated silver… 0.5 Gelatin… 0.5 ExS-6 (sensitizing dye) 1 × 10 ⁻⁴ ExY-9 (DIR coupler)… 0.01 ExY-11 (yellow coupler)… 0.20 ExC-1 (cyan) Coupler) 0.02 Solv-1 (solvent) 0.10 Fifteenth layer (first protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.07μ) Silver coating amount ... 0.12 Gelatin ... 0.9 UV-4 (UV absorber) 0.11 UV-5 (UV absorber) 0.16 Solv-5 (solvent) ... 0.02 H-1 (hardener) 0.13 Cpd-5 (scavenger) ... 0.10 Polyethyl acrylate latex ... 0.09 16th layer (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, spherical equivalent diameter 0.7μ) Coating silver amount ... 0.36 Gelatin ... 0.55 Polymethylmethacrylate particles Diameter 1.5μ ... 0.2 H- 1 (Hardener) 0.17 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0.07 g / m ² ) Surfactant Cpd-4 (0.03 g / m ² ) was added as a coating aid.

Cpd-10 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK When the obtained photographic material was processed by the following processing method, no color remained after processing and a color image was obtained with better color reproduction.

Next, the composition of the treatment liquid will be described.

Color developer (unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyaluminate 2.4- [N-ethyl -N- (β-hydroxyethyl) amino] -2-methylaniline sulphate 4.5 Add water to 1.0 pH 10.05 Bleach-fixing solution (Unit: g) Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (100g /) 240.0ml Ammonia water (27%) 6.0ml Add water 1.0 pH 7.2 Washing solution Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) in a mixed bed column. After passing water, the concentration of calcium and magnesium ions was adjusted to 3 mg / or less, and subsequently 20 mg / of sodium diisocyanurate dichloride and 0.15 g / of sodium sulfate were added. The pH of this solution is in the range 6.5-7.5.

Stabilizer (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added to 1.0 pH 5.0 to 8.0 Example 7 [1] Preparation of tabular silver iodobromide grain emulsion In water 1, potassium bromide 5 g, potassium iodide 0.05 g, gelatin 30 g, thioether HO (CH ₂ ) ₂ S of the following structural formula
(CH ₂ ) ₂ OH 0.125 g was added and kept in an aqueous solution kept at 75 ° C., while stirring, an aqueous solution of silver sulfate 8.33 g and potassium bromide 5.94 g,
An aqueous solution containing 0.726 g of potassium iodide was added over 45 seconds by the double jet method. Then, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 7 minutes and 30 seconds,
The addition was performed so that the flow rate at the end of the addition was double that at the start of the addition. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method for 25 minutes while maintaining the potential at pAg8.1 to grow particles. The flow rate at this time was accelerated so that the flow rate at the end of addition was 8 times the flow rate at the start of addition. After the completion of the addition, 15 cc of 2N potassium thiocyanate solution was added, and further 50 cc of 1% potassium iodide aqueous solution was added over 30 seconds. After this the temperature is set to 35
After lowering the temperature to ℃ and removing soluble salts by precipitation method,
The temperature was raised to 68 ° C., 68 g of gelatin, 2 g of phenol and 7.5 g of trimethylolpropane were added, and the pH was adjusted to 6.40 and pAg 8.45 with sodium hydroxide and potassium bromide.

After raising the temperature to 56 ° C, a sensitizing dye 620m having the following structure
g and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 160 mg. 10 minutes later sodium thiosulfate pentahydrate 8.2 mg potassium thiocyanate 163 mg, chloroauric acid
5.4 mg was added, and after 5 minutes, it was rapidly cooled to solidify. The resulting emulsion consists of grains with an aspect ratio of 3 or more in 93% of the total projected area of all grains, and the average shooting area diameter of all grains with an aspect ratio of 2 or more is 0.83 μm, standard deviation 18.5%, and thickness. The average aspect ratio was 0.161 μm, the average aspect ratio was 5.16, and the average iodine content was 0.8 mol%.

[2] Preparation of emulsion coating solution The following chemicals were added to the emulsion described in [1] per mol of silver halide to prepare a coating solution.

・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 80 mg ・ 1.4-dihydroxy-3-potassium sulphate 9.3 g ・ sodium polyacrylate (average molecular weight 41,000): 4.0 g [ 3] Preparation of coating solution for surface protective layer For coating the surface protective layer, an aqueous solution having the following composition per one side when coating and drying was used.

Gelatin 1.2 g / m ² Dextran 0.4 g / m ² Polyacrylamide 0.4 g / m ² Sodium polyacrylate 0.02 g / m ² Potassium polystyrene sulfonate 0.02 g / m ² Poly (methyl methacrylate / methacrylic acid; molar ratio
9: 1) (particle size 4.3μ) 0.05 g / m ² dimethylsiloxane (dispersed with dodecylbenzenesulfonic acid) (particle size 0.11 μ) 0.03 g / m ² cetyl palmitate (dioctyl sodium α-sulfosuccinate) Particle size 0.10 μ 0.03 g / m ² Colloidal silica 0.15 g / m ² Potassium nitrate 0.06 g / m ² Dioctyl sodium salt of α-sulfosuccinate 0.005 g / m ² Dodecylbenzenesulfonic acid 0.005 g / m ₂ p- Octylphenoxyethoxyethoxy sodium ethoxide sulfonate 0.005g / m ² p-octylphenoxytriglycidyl butane sulfonate 0.005g / m ² Poly (degree of polymerization 10) Oxyethylene cetyl acethle 0.02 g / m ² Poly (degree of polymerization 10) oxyethylene poly (polymerization degree 3) oxy glyceryl octylphenyl ether 0.005 g / m ² poly (polymerization degree 10) oxyethylene poly (degree of polymerization) glyceryl cetyl et Ether 0.005 g / m ² poly (polymerization degree 10) glyceryl dodecyl ether 0.005 g / m
² Poly (degree of polymerization 10) glyceryl p-nonylphenyl ether 0.005g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.03 g / m ² [4] Undercoat layer coating on support Corona discharge on biaxially stretched 175 μm thick polyethylene terephthalate film After the treatment, a first undercoat liquid having the following composition was applied by a wire bar coater so that the applied amount was 5.1 cc / m ^2, and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface.

On this support a solid dispersion of dye I-2 on both sides according to method (1) (Example 1) and a sharp dispersion with sharp absorption according to method (4) was prepared as shown in Table 6
It was applied as a layer.

[5] Preparation of photographic material The emulsion coating solution of [2] and the surface protective layer coating solution of [3] were applied simultaneously on both sides of a polyethylene terephthalate support by the same extrusion method, and dried to obtain a photographic material. did. However, the coating solutions of [2] and [3] were adjusted to pH 6.0.

At this time, the coating silver amount on each side of both materials was 4.0 g / m ²
(2.0 g / m ² per side), and the gelatin coating amount of the surface protective layer per side was 1.2 g / m ² as shown in [3]. All photographic materials also contain 6- (1,2-bis (sulfonylacetamide) ethane as a hardener in the emulsion layer immediately before coating.
It was added at a ratio of mmol / 100 g-gel.

(Photographic performance evaluation) For the exposure of the photographic material, a G-4 screen of GENEX series manufactured by Fuji Photo Film Co., Ltd. was used as a screen. According to a conventional method, photographic materials 1-1 to 1-8 were sandwiched between two G-4 screens so as to be in close contact with each other, and X-ray exposure was carried out through a water fatome 10 cm.

The processing after exposure is performed using a developer manufactured by Fuji Photo Film Co., Ltd.
RD-III at 35 ℃, using the same company Fuji F as the fixer,
An automatic processor processing was performed with the company's FRM-4000.

The sensitivities are shown as relative sensitivities with photographic material 1-8 as 100.

(Measurement of Sharpness (MTF)) The MTF was measured by a combination of the above-described G4 screen and automatic processing. The measurement was performed with an aperture of 30 μm × 500 μm, and the optical density was evaluated at a portion where the optical density was 1.0 using an MTF value with a spatial frequency of 1.0 cycle / mm.

(Evaluation of residual color) The residual color of the processed film was evaluated as follows. The above materials were first processed in an FPM-4000 automatic processor without exposure. However, in order to make the conditions worse, the developing temperature is 31 ° C and the washing water temperature is adjusted by using the used low pH developer.
It was set at 10 ° C. Subsequently, similarly, the unexposed sample was subjected to FPM-4000 treatment for 90 seconds by using a developing solution in a normal state at a developing temperature of 35 ° C., a washing water temperature of 25 ° C. For each material of the former condition, a sample of the corresponding latter condition (a condition in which substantially no residual color is generated) was evaluated with the naked eye using a sample for comparison. The results obtained are shown in Table 6.

As shown in Table 6, the dispersion of the present invention has a sharp absorption in a wavelength region very close to the spectral sensitization region of silver halide grains and a high absorbance. As compared with the case of using the solid dispersion of the method (1), the residual color is the same, but the sharpness is remarkably improved.

Example 8 A paper support (thickness: 10) laminated on both sides with polyethylene
Color photographic light-sensitive material No. 8 was prepared by applying the following first to fourteenth layers on the front side (0 micron) and the back side and fifteenth to sixteenth layers. The polyethylene on the first coating side contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L ^* , 88.0, -0.20 for a ^* and b ^* systems,
It was −0.75. ).

(Composition of photosensitive layer) The components and the coating amount (g / m ² unit) are shown below. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the 14th layer emulsion, a Lippmann emulsion which was not surface chemically sensitized was used.

1st layer (antihalation layer) Black colloid 0.10 Gelatin 0.70 2nd layer (Intermediate layer) Gelatin 0.70 3rd layer (Low sensitivity red sensitive layer) Spectral sensitized with red sensitizing dye (ExS-1, 2, 3) Silver bromide (average grain size 0.25μ, size distribution [variation coefficient]
8%, octahedron) 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (5 mol% silver chloride, average particle size 0.40μ, size distribution 10%, octahedron) ) 0.08 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) 0.18 Anti-staining agent (Cpd-5) 0.003 Coupler dispersion Medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12 4th layer (high sensitivity red sensitive layer) Spectral sensitized with red sensitizing dye (ExS-1, 2, 3) Silver bromide (average grain size 0.60μ, size distribution 15%, octahedron) 0.14 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3) 4 equivalents) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12 Fifth layer (intermediate layer) Gelatin 1.00 Color mixture inhibitor (Cpd-7) 0.08 Color inhibitor solvent (Solv-4, 5 equivalents) 0.16 Polymer latex (Cpd-8) 0.10 6th layer (low sensitivity green sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (Average grain size 0.25μ, size distribution 8%, octahedron) 0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (silver chloride 5 mol%, average grain size 0.40μ, size distribution)
10%, octahedron) 0.06 Gelatin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.11 Anti-fading agent (equal amounts of Cpd-9, 26) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13) 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (ExsS- Silver bromide spectrally sensitized in 4) (average grain size 0.65μ, size distribution 16%, octahedron) 0.10 gelatin 0.80 magenta coupler (ExM-1, 2, 3 equivalents) 0.11 anti-fading agent (Cpd-9 , 26 equivalents) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) ) 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixture inhibitor (Cpd-7) 0.03 Color mixing inhibitor Solvent (Solv-4, 5 equivalents) 0.10 Polymer latex (Cpd-8) 0.07 10th layer (intermediate layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Blue sensitizing dye (ExS Silver bromide spectrally sensitized with -5, 6) (average grain size 0.40μ, size distribution 8%, octahedron) 0.07 Chlorobromination spectrally sensitized with blue sensitizing dye (ExS-5, 6) Silver (8 mol% silver chloride, average grain size 0.60μ, size distribution 11%, octahedron) 0.14 Gelatin 0.80 Yellow coupler (ExY-1, 2 equivalents) 0.35 Antifading agent (Cpd-14) 0.10 Antistain ( Cpd-5,15 in 1: 5 ratio) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 12th layer (high sensitivity blue sensitive layer) Blue sensitizing dye (ExS-5, 6) ) Spectrally sensitized silver bromide (average grain size 0.85μ, size distribution 18%, octahedron) 0.15 gelatin 0.60 yellow coupler (ExY-1, 2 equivalents) 0.30 Anti-fading agent (Cpd-14) 0.10 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 13th layer (UV absorption) Layer) Gelatin 1.00 UV absorber (Cpd-2, 4, 16 equivalents) 0.50 Color mixing inhibitor (Cpd-7, 17 equivalents) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-2, 7 equivalents) Equivalent) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27
10: 10: 13: 15: 20 ratio) 0.05 14th layer (protective layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.1μ)
0.03 Polyvinyl alcohol acrylic modified copolymer (molecular weight
50,000) 0.01 Polymethylmethacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent 0.05 gelatin 1.80 gelatin hardening agent (H-1, H-2 equivalent) 0.18 15th layer (back layer) gelatin 2.50 UV absorber (Cpd-2, 4) , 16 equivalents) 0.50 Dye (equal amounts of Cpd-18, 19, 20, 21, 27) 0.06 16th layer (back surface protection layer) Polymetal methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5 μ) equivalent 0.05 gelatin 2.00 gelatin hardening agent (H-1, H-2 equivalent) 0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate is vigorously added to an aqueous gelatin solution. While stirring, the mixture was added simultaneously at 75 ° C. over 1 minute to obtain octahedral silver bromide grains having an average grain size of 0.35 μm. At this time silver 1
0.3 g per mole of 3,4-dimethyl-1,3-thiazoline-2
-Thion was added. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol of silver were sequentially added, and heated at 75 ° C. for 80 minutes to perform chemical sensitization. The particles thus obtained are used as cores for further growth in the same precipitation environment as the first time, and finally the average particle size is 0.7μ.
Octahedral monodispersed core / shell silver bromide emulsion was obtained. The coefficient of variation of particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion. Obtained.

In each photosensitive layer, ExZK-1 and ExZK-2 were used as image nucleating agents at 10 ^-3 and 10 ^-2 % by weight, respectively, relative to silver halide, and Cpd-22 as a nucleation accelerator was used at 10 ^-2 % by weight. . Further, in each layer, alkanol XC (Dupon Co.) and sodium alkylbenzenesulfonate were used as emulsification / dispersion aids, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. In the layers containing silver halide and colloidal silver, (Cpd-23, 24, 25) was used as a stabilizer. This sample was designated as sample number 8-. The compounds used in the examples are shown below.

Solv-1 di (2-ethylhexyl) sebacate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv-7 di ( 2-Ethylhexyl) phthalate H-1 1,2-bis (vinylsulfonylacetamide)
Ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt ExZK-1 (N-I-27) 7- (3-methoxythiocarbonylaminobenzamide) -10-prohagyl-1 , 2,3,
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 1-formyl-2- {4- [3- {3- [3
-(2,4-di-tert-pentylphenoxy) propyl]
Ureido} phenylsulfonylamino] -phenyl} hydrazine Then, in the yellow filter layer of the ninth layer of Sample 5-, 0.15 g / m ² of the solid dispersion (5) of Example 1 was used as the yellow dye coating amount instead of colloidal silver. Sample 8 was prepared in exactly the same manner except that

Further, in the first antihalation layer of Sample 8-, 0.10 g / m ² of the solid dispersion (1) of Example 1 was used as a dye instead of black colloidal silver, and the following dye was used in the dispersion method of Example 1 (1 Sample No. 8- except that 0.10 g / m ^{2 of} the disperse dye dispersed by the ball mill was applied according to
It was created.

Further, in Sample 8-, Sample 5 was prepared in which the first layer was the same as Sample 8-and the ninth layer was the same as Sample 8-.

The silver halide color photographic light-sensitive materials 8 to prepared as described above were imagewise exposed at 1/10 and 300 CMS and then processed by the following method using an automatic processor. Treatment process time Temperature Mother liquor tank solution Color development 135 seconds 38 ℃ 11 Bleaching fixing 40 seconds 33 ℃ 3 Washing with water (1) 40 seconds 33 ℃ 3 Washing with water (2) 40 seconds 33 ℃ 3 Drying 30 seconds 80 ℃ Composition of each processing solution Was as follows:

Color developer Mother liquor D-sorbit 0.15 g Sodium naphthalenesulfonate / formalin condensate 0.15 g Ethylenediaminetetrakismethylenephosphonic acid 1.5 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.4 g N , N-bis (carboxymethyl) hydrazine 4.0 g D-glucose 2.0 g triethanolamine 6.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline acid salt 6.4 g potassium carbonate 30.0 g Fluorescent brightener (diaminostilbene type) 1.0 g Water added 1000 ml pH (25 ℃) 10.25 Bleach-fixer mother liquor ethylenediaminetetraacetic acid ・ 2 sodium ・ dihydrate 2.0 g ethylenediaminetetraacetic acid ・ Fe (III)・ Ammonium ・ dihydrate 70.0 g Ammonium thiosulfate (700 g /) 180 ml Sodium p-toluenesulfinate 45.0 g Sodium bisulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Add water to 1000 ml pH (25 ° C) 6.10 Wash water Tap water Calcium and magnesium ions are passed through a mixed bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). The concentration was treated to 3 mg / or less, and subsequently, sodium isocyanurate dichloride 20 mg / and sodium sulfate 0.15 g / were added. The pH of this solution was in the range of 6.5-7.5.

As a result of measuring the minimum density (Dmin) of the treated sample, a remarkable difference was observed between the blue light (B) density and the red light (R) density in each sample.

The results are shown in Table 7. When Dye solid is used in place of colloidal silver, the characteristic that Dmin is close is obtained. Also
The sample 8 using the solid solid dispersion of Sharp absorption had a green sensitivity increase of 0.04 for the sample 8-8 and the sample 8-4 for the sample 8-8.

Example 9 Dispersions of the dispersion according to the dispersion method (1) and the dispersion according to the dispersion method (4) of Example 1 were respectively diluted with water, placed on a carbon vapor-deposited mesh, dried, washed with water and dried again. Then, a sample for electron diffraction was prepared.

Using a transmission electron microscope (JEOL2000FX manufactured by JEOL Ltd.) with N ₂ stage, the above sample has a camera length of 100c.
The electron diffraction pattern was photographed at m.

The electron diffraction patterns of both are clearly different, and it can be seen that both have different crystal structures.

Besides the embodiments described in detail herein, Japanese Patent Application No. 1-14
A similar effect was obtained as a result of changing and testing the dye solid dispersion in the photosensitive material as described in Example 5, Example 6, Ex. 2 and the like of 2683 specification.

(Effect of the Invention) According to the present invention, when used in an antihalation layer, the coating amount of a dye can be reduced, or the sensitivity of other layers can be prevented from being lowered, and if the dye coating amount is the same, sharpening can be achieved. The degree of improvement is improved, the residual color is reduced, or the sensitivity of other layers is not decreased. It was also confirmed that when used as a filter layer, the color reproduction was good and the decolorizing property was improved, and the intended effects were improved.

[Brief description of drawings]

FIG. 1 is a photograph of an electron beam diffraction pattern taken in Example 9 for a solid dispersion prepared by the conventional mechanical dispersion method (1) of Example 1. FIG. 2 is a photograph of the electron beam diffraction pattern taken in Example 9 for the solid dispersion prepared by the precipitation dispersion method (4) according to the present invention in Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-197943 (JP, A) JP-A-52-92716 (JP, A) Special table 1-502912 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic emulsion layer and another hydrophilic colloid layer are provided on a support, and the silver halide emulsion layer or the other hydrophilic colloid layer is represented by the general formula (I) or (II). In the silver halide photographic light-sensitive material containing the dye represented by the solid dispersion, the solid dispersion of the dye is a fine solid precipitated by lowering the pH of the alkaline aqueous solution of the dye and the protective colloid,
A silver halide photographic light-sensitive material characterized by having a half-value width of its absorption spectrum of 90 nm or less. General formula (I) In the formula, R ₁₁ represents an aryl group or an aralkyl group having at least one carboxylic acid group, R ₁₂ represents an alkyl group,
Aryl group, aralkyl group, cyano group, -COOR ₁₇ , -CO
NR ₁₇ R ₁₈ , -COR ₁₉ , -SO ₂ R ₁₉ , -SO R ₁₉ , -SO ₂ NR ₁₇ R
₁₈ , -OR ₁₇ , -NR ₁₇ R ₁₈ , -NR ₁₈ COR ₁₉ , -NR ₁₇ CONR ₁₇ R
₁₈ or -NR ₁₈ SO ₂ R ₁₉ (wherein R ₁₇ and R ₁₈ are hydrogen atoms,
Represents an alkyl group, an aralkyl group or an aryl group, R
₁₉ represents an alkyl group, an aralkyl group or an aryl group, and R ₁₇ and R ₁₈ or R ₁₈ and R ₁₉ may be connected to each other to form a 5- or 6-membered ring. R ₁₃ and R ₁₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ₁₇ , —NR ₁₇ R
_{18, - NR 18 COR 19,} -COOR 17, -CONR 17 R 18 ( wherein,
R ₁₇ , R ₁₈ and R ₁₉ have the same meaning as R ₁₇ , R ₁₈ and R ₁₉ defined above. ), R ₁₅ and R ₁₆ are a hydrogen atom, an alkyl group,
Aralkyl group, alkenyl group, aryl group, acyl group,
Or a sulfonyl group, R ₁₅ and R ₁₆ may be linked to form a 5- or 6-membered ring, and R ₁₃ and R ₁₅ or R ₁₄ and R ₁₆ may be linked to form a 5- or 6-membered ring. May be. L ₁₁ , L ₁₂ , and L ₁₃ each represent a methine group, and n is 0 or 1.
Represents General formula (II) In the formula, R ₂₁ and R ₂₃ each have the same meaning as R ₁₁ in formula (I), and R ₂₂ and R ₂₄ each have the same meaning as R ₁₂ in formula (I). L ₂₁ , L ₂₂ , and L ₂₃ each represent a methine group, and m
Represents 0, 1 or 2.