Silver halide photographic material

Disclosed is a silver halide photographic material having a hydrophilic colloid layer which contains a dispersion of solid fine grains of an oxonole dye which does not have any dissociating proton-containing substituent or salt thereof capable of dissolving the dye during development, except the enolic proton constituting a part of the chromophoric group of the dye in the compound. In the photographic material, the oxonole dye colors only the specific hydrophilic layer without having any bad effect on the photographic properties of the material. The dye may be rapidly decolored by development of the material.

FIELD OF THE INVENTION 
The present invention relates to a silver halide photographic material 
containing a dispersion of solid fine grains of a novel compound (i.e., 
compound dispersed in the form of solid fine grains). 
BACKGROUND OF THE INVENTION 
In a silver halide photographic material, coloration of the photographic 
emulsion layers and other hydrophilic colloid layers constituting the 
material is often modified for the purpose of controlling the spectral 
composition of the light to be applied to the material or for the purpose 
of preventing halation or irradiation of the material. It is necessary 
only that the layer to which the dye has been added is selectively colored 
therewith in order that the dye does not impart any harmful spectral 
effect to the other layers and that the dye sufficiently displays filter, 
anti-halation and anti-irradiation effects. However, when the layer to 
which the dye has been added is kept in contact with other hydrophilic 
colloid layers in a wet condition, a part of the dye often diffuses from 
the former to the latter. In order to prevent such diffusion of the dye, 
various efforts have heretofore been made. 
For instance, a method of coloring a specific layer with solid fine grains 
of a water-insoluble dye is illustrated in JP-A-56-12639, JP-A-55-155350, 
JP-A-55-155351, JP-A-63-197943, European Patents 15,601, 274,723, 276,566, 
and 299,435, U.S. Pat. No. 4,803,150, and International Patent Application 
Laid-Open No. (WO)88/04794. (The term "JP-A" as used herein means an 
"unexamined published Japanese patent application".) 
Specifically, a method using solid fine grains of an oxonole dye is 
illustrated in JP-A-52-92716, JP-A-55-120030, JP-A-63-27838, 
JP-A-64-40827, JP-A-2-277044, JP-A2-282244, JP-A-3-23441, JP-A-3-208044, 
JP-A-3-192250, JP-A-3-194544, JP-A-3-200248, JP-A-3-204639, JP-A-3-204640, 
JP-A-3-206441, JP-A-3-206442, JP-A-3-208042, JP-A-3-208043, and 
JP-A-3-213847. 
The improved methods still suffer from various problems. The decoloration 
rate in development is low so that the disclosed techniques do not 
satisfactorily modify the characteristics of the photographic materials. 
For instance, when a photographic material is processed by rapid 
processing or with a modified processing solution, or when the composition 
of the photographic emulsion constituting a photographic material is 
modified, the decoloring function is not always sufficiently displayed or 
the dye incorporated into the photographic material often has a bad 
influence on the photographic properties of the material. 
SUMMARY OF THE INVENTION 
One object of the present invention is to provide a photographic material 
containing a dye which may color a specific hydrophilic colloid layer in 
the material and which may be decolored rapidly during development of the 
material. Another object of the present invention is to provide a 
photographic material containing a dye which may color a specific 
hydrophilic colloid layer in the material and which may be decolored 
rapidly during development of the material without having any bad 
influence on the photographic emulsions constituting the material. 
The present inventors have found that these and other objects may be 
attained by a silver halide photographic material comprising a support 
being containing a hydrophilic colloid layer which contains a dispersion 
of solid fine grains of a compound of the following formula (I): 
EQU A.sub.1 =L.sub.1 -L.sub.2).sub.m L.sub.3 (L.sub.4 =L.sub.5).sub.n 
A.sub.2(I) 
wherein A.sub.1 and A.sub.2 each represents an acidic nucleus necessary for 
forming an oxonole dye, excepting the case where A.sub.1 and A.sub.2 are 
both 2-pyrazolin-5-one nuclei, the case where they are both barbituric 
acid nuclei, and the case where .they are both 2,6(1H,3H)-pyridinedione 
nuclei; L.sub.1, L.sub.2, L.sub.3, L.sub.4 and L.sub.5 each represents a 
methine group; and m and n each represents 0, 1 or 2; provided that the 
compound does not have any dissociating proton-containing substituent or 
salt thereof capable of dissolving the compound during development, except 
for the enolic proton such as a hydroxyl group constituting a part of the 
chromophoric group of an oxonole dye. 
Specific examples of dissociating proton-containing substituent or salt 
thereof include a sulfonic acid group, a phosphoric acid group, a 
carboxylic acid group, a sulfonamido group having from 1 to 10 carbon 
atoms (e.g., methanesulfonamido, decanesulfonamido, butanesulfonamido, 
hexanesulfonamide, isobutanesulfonamido, benzenesulfonamido, 
octanesulfonamido), an arylsulfamoyl group having from 6 to 10 carbon 
atoms (e.g., phenylsulfamoyl, naphthylsulfamoyl, tolylsulfamoyl), an 
acylsulfamoyl group having from 1 to 10 carbon atoms (e.g., 
acetylsulfamoyl, butanoylsulfamoyl, octanoylsulfamoyl, decanoylsulfamoyl, 
benzoylsulfamoyl), a sulfonylcarbamoyl group having from 2 to 11 carbon 
atoms (e.g., methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, 
hexanesulfonylcarbamoyt, decanesulfonylcarbamoyl, 
benzenesulfonylcarbamoyl), and a salt thereof (e.g., an inorganic salt of 
Li, Na, K, NH.sub.3, an organic amine salt of triethylamine, 
tetrabutylammonium, pyridine).

DETAILED DESCRIPTION OF THE INVENTION 
Compounds of formula (I) are described in detail hereunder. 
The acidic nucleus represented by A.sub.1 or A.sub.2 is preferably a cyclic 
ketomethylene compound residue or a ketomethylene compound residue 
substituted by electron-attracting groups. Especially preferred is the 
case where at least one of A.sub.1 and A.sub.2 represents a 
pyrazolo[3,4-b]pyridine-3,6-dione nucleus or a 2(5H)-furanone nucleus. 
Specific examples of the nucleus are shown below, as keto forms or their 
analogues: 
##STR1## 
In these formulae, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represents an 
alkyl group, an aryl group, a heterocyclic group or an alkenyl group; and 
R.sub.5, R.sub.6 and R.sub.7 each represents a hydrogen atom or a 
substituent. R.sub.1 and R.sub.2, R.sub.3 and R.sub.4, or R.sub.5 and 
R.sub.6 may be bonded to each other to form a 5-membered or 6-membered 
ring. 
The substituents in these formulae are not specifically limited, provided 
that they do not substantially dissolve the compound of formula (I) in 
water having pH of from 5 to 7 such as a sulfonic acid group and a salt 
thereof, a phosphoric acid group and a salt thereof, or a carboxylic acid 
group and a salt thereof. For instance, suitable substituents include an 
alkyl group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, 
isopropyl, butyl, hexyl, octyl, 2-hydroxyethyl), an alkoxy group having 
from 1 to 8 carbon atoms (e.g., methoxy, ethoxy, butoxy), a halogen atom 
(e.g., chlorine, bromine, fluorine), an amino group having from 0 to 10 
carbon atoms (e.g., dimethylamino, diethylamino, cyanoethylamino), an 
ester group having from 2 to 10 carbon atoms (e.g., methoxycarbonyl, 
ethoxycarbonyl, phenoxycarbonyl), an amido group (e.g., acetylamino, 
benzamido), a carbamoyl group having from 1 to 10 carbon atoms (e.g., 
methylcarbamoyl, ethylcarbamoyl), a sulfamoyl group having from 0 to 10 
carbon atoms (e.g., methylsulfamoyl, butylsulfamoyl), an aryl group having 
from 6 to 10 carbon atoms (e.g., phenyl, naphthyl, 4-methoxyphenyl, 
3-methylphenyl), an acyl group having from 2 to 10 carbon atoms (e.g., 
acetyl, benzoyl, propanoyl), a sulfonyl group having from 1 to 10 carbon 
atoms (e.g., methanesulfonyl, benzenesulfonyl), a ureido group having from 
1 to 10 carbon atoms (e.g., ureido, methylureido), a urethane group having 
from 2 to 10 carbon atoms (e.g., methoxycarbonylamino, 
ethoxycarbonylamino), a sulfonate group (e.g., methoxysulfonyl, 
phenoxysulfonyl), a cyano group, a hydroxyl group, a nitro group, and a 
heterocyclic group (e.g., benzoxazole ring, pyridine ring, sulforan ring, 
furan ring). 
The alkyl group represented by R.sub.1, R.sub.2, R.sub.3 or R.sub.4 is 
preferably an alkyl group having from 1 to 10 carbon atoms (e.g., methyl, 
ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, 
nonyl) which may optionally have substituent (s) (such as those mentioned 
above, excepting an alkyl group). 
The aryl group represented by R.sub.1, R.sub.2, R.sub.3 or R.sub.4 is 
preferably an aryl group having from 6 to 10 carbon atoms (e.g., phenyl, 
naphthyl) which may have substituent(s) (such as those mentioned above). 
The heterocyclic group represented by R.sub.1, R.sub.2, R.sub.3 or R.sub.4 
is preferably a 5-membered or 6-membered heterocyclic group (e.g., oxazole 
ring, benzoxazole ring, thiazole ring, imidazole ring, pyridine ring, 
furan ring, thiophene ring, sulforan ring, pyrazole ring, pyrrole ring, 
chroman ring, coumarin ring) which may have substituent(s) (such as those 
mentioned above). 
The alkenyl group represented by R.sub.1, R.sub.2, R.sub.3 or R.sub.4 is 
preferably an alkenyl group having from 2 to 10 carbon atoms (e.g., vinyl, 
allyl, 1-propenyl, 2-pentenyl, 1,3-butadienyl). 
R.sub.1 and R.sub.2, R.sub.3 and R.sub.4, or R.sub.5 and R.sub.6 may be 
bonded to each other to form a ring, which is preferably a 5-membered or 
6-membered ring such as a pyrrolidine ring, a piperidine ring, a 
morpholine ring or a benzene ring. 
The methine group represented by L.sub.1, L.sub.2, L.sub.3, L.sub.4 and 
L.sub.5 may optionally have substituent(s) (e.g., methyl and ethyl group 
and a halogen atom). As the case may be, the substituents on the group may 
be bonded to each other to form a 5-membered or 6-membered ring (for 
example, cyclopentene ring, cyclohexene ring, isophorone ring). The 
methine group is preferably unsubstituted. 
Specific examples of dyes of formula (I) are shown below, which, however, 
are not to be considered as limiting the invention. 
##STR2## 
Among these, especially preferred are (I-2), (I-5) to (I-11), (I-36), and 
(I-38). 
Compounds of formula (I) may be produced by conventional methods known by 
those skilled in the art. For instance, they may be produced by 
condensation of the corresponding acidic nucleus and a methine source such 
as ethyl orthoformate, diphenylamidine, 1,1,3,3-tetramethoxypropane, 
malonaldehyde-dianil or glutaconaldehyde-dianil. Specifically, they are 
produced by the methods described in JP-A-52-92716, JP-A-55-120030, 
JP-A-63-27838, JP-A-64-40827, JP-A-2-277044, JP-A-2-282244, JP-A-3-23441, 
JP-A-3-208044, JP-A-3-192250, JP-A-3-194544, JP-A-3-200248, JP-A-3-204639, 
JP-A-3-204640, JP-A-3-206441, JP-A-3-206442, JP-A-3-208042, JP-A-3-208043, 
and JP-A-3-213847. 
Dispersion of compounds of formula (I) may be effected by any milling 
method (for example, with a ball mill, a shaking ball mill, a planet ball 
mill, a sand mill, a colloid mill, a jet mill, a roller mill). The use of 
a solvent (e.g. water) is preferred, and the use of a surfactant for 
dispersion is more preferred. After the compound of formula (I) of the 
present invention is dissolved in a suitable solvent, a poor solvent for 
the compound may be added to the resulting solution so as to precipitate 
fine crystals. Also, a surfactant for dispersion may be used. 
Alternatively, the compound is first dissolved in a solvent under a 
controlled pH value of the system, and thereafter the pH value thereof may 
be varied to give fine crystals in the system. 
Fine grains of the compound of the present invention in the dispersion are 
desired to have a mean grain size from 0.005 .mu.m to 10 .mu.m, preferably 
from 0.01 .mu.m to 1 .mu.m, more preferably from 0.01 .mu.m to 0.5 .mu.m, 
especially preferably from 0.01 .mu.m to 0.1 .mu.m. 
For dispersion of the compound of formula (I), heating may be effected 
before and/or after dispersion. For the purpose of more effectively 
heating the dispersion system, heating is effected at least after 
dispersion. 
The heating method is not specifically limited, provided that the solid dye 
may be directly heated. The temperature is preferably 40.degree. C. or 
higher. The uppermost limit of the heating temperature is not specifically 
limited but is preferably 250.degree. C. or lower. More preferably, the 
heating temperature is from 50.degree. C. to 150.degree. C. 
The heating time also is not specifically limited, provided that the dye is 
not decomposed by heating. It may be from 15 minutes to 1 week, preferably 
from 1 hour to 4 days. 
For effectively performing the heat treatment, the heating is preferably 
performing in a solvent. The kind of the solvent to be used for this 
purpose is not specifically limited, provided that it does not 
substantially dissolve the dye of formula (I). For instance, suitable 
solvents include water, alcohols (e.g. methanol, ethanol, isopropyl 
alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol, diethytene 
glycol ethyl cellosolve), ketones (e.g., acetone, methyl ethyl ketone), 
esters (e.g., ethyl acetate, butyl acetate), alkylcarboxylic acids (e.g., 
acetic acid, propionic acid), nitriles (e.g., acetonitrile), and ethers 
(e.g., dimethoxyethane, dioxane, tetrahydrofuran). 
Where an organic carboxylic acid is added to the dispersing system during 
heating it, the effect of the present invention may be attained more 
favorably. Examples of organic carboxylic acids suitable for the purpose 
include alkylcarboxylic acids (e.g., acetic acid, propionic acid), 
carboxymethyl celluloses (e.g., CMC), and arylcarboxylic acids (e.g., 
benzoic acid, salicylic acid). 
The amount of the organic carboxylic acid in the system may be from 0.5 to 
100 times of the weight of the compound of formula (I) therein, when it 
acts as a solvent. Where an organic carboxylic acid is added to the system 
in addition to a solvent other than organic carboxylic acids for the 
system, the amount of the acid may be from 0.05 to 100% by weight to the 
weight of the compound of formula (I) in the system. 
The amount of the compound of formula (I) in the photographic material of 
the present invention may be any desired effective amount. It is 
preferably such that the optical density on one surface of the 
photographic material may fall within the range of from 0.05 to 3.0. 
Specifically, the amount on one surface of the compound represented by 
formula (I) used is preferably from 0.5 mg/m.sup.2 to 1,000 mg/m.sup.2, 
more preferably from 1 mg/m.sup.2 to 500 mg/m.sup.2. The time for adding 
the compound of formula (I) to the photographic material may be any time 
before coating. 
The compound of formula (I) may be added to the emulsion layer or to any 
other hydrophilic colloid layer (e.g., interlayer, protective layer, 
anti-halation layer, filter layer, subbing layer) constituting the 
photographic material. It may be added to a single layer or a plurality of 
layers constituting the photographic material. 
The typical hydrophilic colloid in the photographic material of the present 
invention is gelatin. In addition, any other which has heretofore been 
known as being suitable for photographic materials may be used. 
The silver halide emulsion constituting the photographic material of the 
present invention is preferably an emulsion of silver bromide, silver 
iodide, silver iodobromide, silver iodochlorobromide, silver chlorobromide 
or silver chloride. 
The silver halide grains in the emulsion may be regular crystalline such as 
cubic or octahedral grains, or irregular crystalline such as spherical or 
tabular grains. They may also be composite grains composed of regular and 
irregular crystalline forms. A mixture comprising different crystalline 
grains may also be used in the present invention. However, regular 
crystalline grains are preferred. 
Regarding the silver halide grains, photographic emulsions and methods of 
producing them, as well as the binders or protective colloids, the 
hardening agents, the sensitizing dyes and the stabilizers or antifoggants 
in the photographic material of the present invention, those mentioned in 
JP-A-3-238447, from page 18, left bottom column, line 18 to page 20, left 
bottom column, line 17 are referred to. 
The photographic material of the present invention may contain one or more 
surfactants for the purposes of aiding coating, prevention of static 
charges, improvement of sliding property, improvement of emulsification or 
dispersion, prevention of adhesion and improvement of photographic 
properties (e.g., elevation of developability, elevation of contrast, 
sensitization). 
The photographic material of the present invention may also contain any dye 
other than the dyes of the present invention in the hydrophilic colloid 
layers constituting the material, as a filter dye or for anti-irradiation 
or anti-halation or for various other purposes. As such dyes, preferred 
are oxonole dyes, hemioxonole dyes, styryl dyes, merocyanine dyes, 
anthraquinone dyes, and azo dyes. In addition, also suitable are cyanine 
dyes, azomethine dyes, triarylmethane dyes and phthalocyanine dyes. If 
these dyes are soluble in water, they may be added to the layers in the 
form of a solution. If they are hardly soluble in water, they may be added 
thereto as a dispersion of solid fine grains. Oil-soluble dyes may be 
added to the layer in the form of an emulsion by an oil-in-water 
dispersion method. 
The techniques for making and using multi-layer, multi-color photographic 
materials, supports, methods of coating photographic emulsion layers, 
means of exposing photographic materials and means of photographic 
processing of photographic materials, which are described in 
JP-A-3-238447, from page 20, right bottom column, line 14 to page 27, 
right top column, line 2, may apply to the present invention. 
The present invention will be explained in more detail by way of the 
following examples, which, however, are not intended to restrict the scope 
of the present invention. 
EXAMPLE 1 
Preparation of Tabular Grains 
Six g of potassium bromide and 7 g of gelatin were added to one liter of 
water and heated up to 55.degree. C. in a container. To this mixture were 
added 37 cc of an aqueous solution of silver nitrate (containing 4.00 g of 
silver nitrate) and 38 cc of an aqueous solution containing 5.9 g of 
potassium bromide with stirring, by a double jet method over a period of 
37 seconds. 18.6 g of gelatin was added thereto, and the mixture was 
heated up to 70.degree. C. To this mixture was added 89 cc of an aqueous 
solution of silver nitrate (containing 9.8 g of silver nitrate) over a 
period of 22 minutes. Seven cc of a 25% aqueous ammonia solution was added 
thereto, and physical ripening of the system was effected for 10 minutes 
at the elevated temperature. Then, 6.5 cc of a 100% acetic acid solution 
was added thereto. Subsequently, an aqueous solution containing 153 g of 
silver nitrate and an aqueous solution of potassium bromide were added 
thereto, while the pAg of the system was kept at 8.5 by a controlled 
double jet method over a period of 35 minutes. Next, 15 cc of a 2 N 
solution of potassium thiocyanate was added thereto. The system was thus 
subjected to physical ripening for 5 minutes at the elevated temperature, 
and thereafter the temperature of the system was lowered to 35.degree. C. 
Accordingly, monodispersed pure silver bromide tabular grains, having a 
mean projected area diameter of 1.10 .mu.m, a mean thickness of 0.165 
.mu.m, and a fluctuation coefficient of the diameter of 185% were 
obtained. 
Soluble salts were removed from the emulsion by flocculation. The emulsion 
was again heated up to 40.degree. C., and 30 g of gelatin, 2.35 g of 
phenoxyethanol and, as a thickener, 0.8 g of sodium polystyrenesulfonate 
were added thereto. The emulsion was then adjusted to a pH of 5.90 and pAg 
of 8.25, by adding sodium hydroxide and a silver nitrate solution thereto. 
The emulsion was then chemically sensitized in the manner mentioned below, 
with stirring at 56.degree. C. 
Precisely, 0.043 mg of thiourea dioxide was first added to the emulsion, 
which was kept as it was for 22 minutes for reduction sensitization. Next, 
20 mg of hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 400 mg of the 
following sensitizing dye were added thereto: 
##STR3## 
Further, 0.83 g of calcium chloride was added thereto. Subsequently, 1.3 
mg of sodium thiosulfate, 2.7 mg of Selenium Compound (1) shown below, 2.6 
mg of chloroauric acid and 90 mg of potassium thiocyanate were added 
thereto. Forty minutes after the final addition, the emulsion was cooled 
to 35.degree. C. Thus, the preparation of tabular grains (T-1) was 
completed. 
##STR4## 
Preparation of Coated Sample 
The following chemicals were added to (T-1 ) to prepare a coating solution, 
the amounts of each being per mol of silver halide of (T-1). The coating 
solution was coated on a support to give a coated sample. 
______________________________________ 
Component Amount 
______________________________________ 
Gelatin (including gelatin in emulsion) 
65.5 g 
Trimethylolpropane 9 g 
Dextran (mean molecular weight: 39,000) 
18.5 g 
Sodium Polystyrenesulfonate 
1.8 g 
(mean molecular weight: 600,000) 
Hardening Agent 
(1,2-bis(vinylsulfonylacetamido)ethane: 
to make the swelling percentage 230%) 
##STR5## 34 mg 
##STR6## 4.8 g 
______________________________________ 
A coating solution for a surface protective layer was prepared from the 
following components: 
______________________________________ 
Component Amount 
______________________________________ 
Gelatin 0.966 g/m.sup.2 
Sodium Polyacrylate 0.023 g/m.sup.2 
(mean molecular weight: 400,000) 
4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene 
0.015 g/m.sup.2 
##STR7## 0.013 g/m.sup.2 
##STR8## 0.045 g/m.sup.2 
##STR9## 0.0065 g/m.sup.2 
##STR10## 0.003 g/m.sup.2 
##STR11## 0.001 g/m.sup.2 
##STR12## 1.7 mg/m.sup.2 
Polymethyl Methacrylate 0.087 g/m.sup.2 
(mean grain size 3.7 .mu.m) 
Proxel 0.0005 g/m.sup.2 
(adjusted to a pH of 7.4 with NaOH) 
______________________________________ 
Preparation of Support 
(1) Preparation of Dye Dispersion (D-1) for Subbing Layer 
Dye (I-2) of the present invention was treated with a ball mill in the 
manner described below. 
434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 
surfactant (TX-200) were put in a 2-liter ball mill. Twenty g of Dye (I-2) 
was added to the solution. Four hundred ml of zirconium oxide (ZrO) beads 
(diameter, 2 mm) were added thereto, and the content was milled in the 
mill for 4 days. Next, 160 g of 12.5% gelatin solution was added thereto. 
After defoaming, ZrO beads were removed by filtration. The thus obtained 
dye dispersion was observed to reveal that the grain size distribution of 
the dispersed dye grains fell within the range of from 0.05 to 1.15/.mu.m 
as the diameter and that the mean grain size of the grains was 0.37 .mu.m. 
By centrifugation, large dye grains having a grain size of 0.9 .mu.m or 
more were removed. 
Thus, dye dispersion (D-1) was obtained. 
(2) Preparation of Support 
A biaxially stretched polyethylene terephthalate film having a thickness of 
183 .mu.m was subjected to corona discharging treatment. A first coating 
solution having the composition mentioned below was coated on one surface 
of the film in a coated amount of 5.1 cc/m.sup.2 by wire bar coater. This 
coated film was then dried at 175.degree. C. for one minute. 
The other surface was also coated in the same manner to provide a first 
subbing layer on both surfaces of the film. The polyethylene terephthalate 
used contained 0.04% by weight of a dye having the following structure: 
##STR13## 
______________________________________ 
Composition of Coating Liquid for First Subbing Layer: 
Component Amount 
______________________________________ 
Butadiene-styrene Copolymer Latex 
79 cc 
Solution (solid content 40%; 
butadiene/styrene = 31/69, by weight) 
Latex solution contained the following 
emulsion dispersing agent in an amount 
of 0.4% by weight to the solid content 
of the solution: 
Sodium 2,4-Dichloro-6-hydroxy-s- 
20.5 cc 
triazine (4% solution) 
Distilled Water 900.5 cc 
______________________________________ 
A coating solution having the composition mentioned below was coated on 
both surfaces, each coated with the preceding first subbing layer, by wire 
bar coater to form a second subbing layer thereon. This coated film was 
dried at 150.degree. C. 
______________________________________ 
Composition of Coating Liquid for Second Subbing Layer: 
Component Amount 
______________________________________ 
Gelatin 160 mg/m.sup.2 
Dye Dispersion (D-1) 35 mg/m.sup.2 
(as solid 
content) 
##STR14## 8 mg/m.sup.2 
##STR15## 0.27 mg/m.sup.2 
Matting Agent 2.5 mg/m.sup.2 
(polymethyl methacrylate with mean 
grain size of 2.5 .mu.m) 
______________________________________ 
Preparation of Photographic Material Samples 
The preceding emulsion layer and surface protective layer were coated on 
both surfaces of the previously prepared support by simultaneous 
extrusion, to give photographic material Sample (1-1). Photographic 
material Samples (1-2) to (1-9) were prepared in the same manner as above, 
except that the dyes indicated in Table 1 below was used in preparing the 
dye dispersion of solid fine grains in the second subbing layer. 
For each sample, the amount of silver coated on one surface was 1.75 
g/m.sup.2. 
TABLE 1 
______________________________________ 
Photographic Amount Coated 
Material (on one surface) 
Sample Dye (mg/m.sup.2) 
______________________________________ 
1-1 (Invention) 
I-2 35 
1-2 (Invention) 
I-9 35 
1-3 (Invention) 
I-15 35 
1-4 (Invention) 
I-20 35 
1-5 (Invention) 
I-27 35 
1-6 (Invention) 
I-32 35 
1-7 (Comparison) 
Comparative Dye 
35 
1 
1-8 (Comparison) 
Comparative Dye 
35 
2 (*) 
1-9 (Comparison) 
-- -- 
______________________________________ 
(*) Comparative Dye 2 was dissolved into a uniform solution. 
##STR16## 
Evaluation of Photographic Properties of Samples 
GRENEX Orthoscreen HR-4 (manufactured by Fuji Photo Film Co., Ltd.) was 
closely attached to one surface of each sample by a cassette to carry out 
X-ray sensitometry of the sample. Adjustment of the amount of exposure to 
the sample was effected by varying the distance between the X-ray tube and 
the cassette. After exposure, the exposed sample was processed with an 
automatic developing machine, using the following developer and fixer. The 
sensitivity of each sample was determined as a relative sensitivity to the 
sensitivity of Sample (1-9) as 100. 
Measurement of Sharpness (MTF) 
MTF of each sample was measured by the preceding cassette (HR-4 screen was 
attached to both surfaces) and an automatic developing machine. =The 
measurement was effected with an aperture of 30 .mu.m.times.500 .mu.m. 
Using the MTF value with a space frequency of 1.0 cycle/mm, evaluation was 
effected in the part having an optical density of 1.0. 
Measurement of Color Retention 
Each non-exposed sample was processed with the above-mentioned automatic 
developing machine, and the green transmission density of the processed 
sample was measured with a Macbeth Status A filter. On the other hand, the 
green transmission density of a subbing layer-free blue-colored 
polyethylene terephthalate film support was measured. By subtracting the 
latter density value (of the subbing layer-free support) from the former 
density value (of the processed sample), a color retention density value 
was obtained for evaluation of the sample. 
The automatic developing machine used in the experiment was a modified one 
from FPM-9000 Model (manufactured by Fuji Photo Film Co., Ltd.), in which 
drying is effected by infrared drying. The processing steps in the 
modified machine are shown in Table 2 below. The mean amount of samples 
processed a day was about 200 sheets of a quarto-paper (10 inch.times.12 
inch) size. 
TABLE 2 
______________________________________ 
Amount of 
Processing 
Processing 
Processing 
Processing 
Solution Temper- Path Processing 
Step in Tank ature Length Time 
______________________________________ 
Develop- 15 liters 35.degree. C. 
613 mm 8.8 sec 
ment (ratio of 
surface 
area to 
capacity = 
25 
cm.sup.2 /liter) 
Fixation 15 liters 32.degree. C. 
539 mm 7.7 sec 
Rinsing 13 liters 17.degree. C. 
263 mm 3.8 sec 
(running 
water) 
Squeezing 304 mm 4.4 sec 
Drying 58.degree. C. 
368 mm 5.3 sec 
Total 2087 mm 30.0 sec 
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The compositions of the processing solutions used above are set forth 
below. Replenishment of the processing tanks was effected in the manner 
mentioned below. 
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Preparation of Concentrated Processing Solution: 
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Developer: 
Part Agent (A): 
Potassium Hydroxide 330 g 
Potassium Sulfite 630 g 
Sodium Sulfite 255 g 
Potassium Carbonate 90 g 
Boric Acid 45 g 
Diethylene Glycol 180 g 
Diethylenetriaminepentaacetic 
30 g 
Acid 
1-(N,N-diethylamino)ethyl-5- 
0.75 g 
mercaptotetrazole 
Hydroquinone 450 g 
4-Hydroxymethyl-4-methyl-1- 
40 g 
phenyl-3-pyrazolidone 
Water to make 4125 ml 
Part Agent (B): 
Diethylene Glycol 525 g 
3,3'-Dithiobishydrosuccinic Acid 
3 g 
Glacial Acetic Acid 102.6 g 
5-Nitroindazole 3.75 g 
1-Phenyl-3-pyrazolidone 65 g 
Water to make 750 ml 
Part Agent (C): 
Glutaraldehyde (50 wt/wt %) 
150 g 
Potassium Bromide 15 g 
Potassium Metabisulfite 105 g 
Water to make 750 ml 
Fixer: 
Ammonium Thiosulfate 3000 ml 
(70 wt/vol %) 
Disodium Ethylenediaminetetra- 
0.45 g 
acetate Dihydrate 
Sodium Sulfite 225 g 
Boric Acid 60 g 
1-(N,N-dimethylamino)-ethyl-5- 
15 g 
mercaptotetrazole 
Tartaric Acid 48 g 
Glacial Acetic Acid 675 g 
Sodium Hydroxide 225 g 
Sulfuric Acid (36 N) 58.5 g 
Aluminum Sulfate 150 g 
Water to make 600 ml 
pH 4.68 
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Preparation of Processing Solutions 
The respective part agents (A), (B) and (C) of the preceding concentrated 
developer stocks were separately put in different part containers, which 
were connected to each other by a container system. 
The concentrated fixer was also put in a container of the same kind. 
As a starter, 300 ml of an aqueous solution containing 54 g of acetic acid 
and 55.5 g of potassium bromide was added to the developer tank. 
The developer stock container system containing the above part agents was 
set upside down on the developing machine, with the mouth of each part 
container being inserted into the perforating blade as equipped on the 
side wall of the machine to break the seal film of the cap of the 
container whereby the part agents entered the developer stock tanks. 
The respective part agents were thus introduced into the developer tank and 
the fixer tank of the automatic developing machine in the determined ratio 
mentioned below, by driving the pumps as equipped to the machine. 
At every processing of 8 sheets of quarto-paper (10 inch.times.12 inch) 
size photographic material sample, a mixture of the part agents and water 
of the determined ratio was replenished to each processing tank. 
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Developer: 
Part Agent (A) 55 ml 
Part Agent (B) 10 ml 
Part Agent (C) 10 ml 
Water 125 ml 
pH 10.50 
Fixer: 
Concentrated Fixer 80 ml 
Water 120 ml 
pH 4.62 
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The rinsing tank was filled with tap water. The results obtained are shown 
in Table 3 below. 
TABLE 3 
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Relative 
Photographic Sensitivity 
Material (front Color 
Sample Dye surface) MTF Retention 
______________________________________ 
1-1 I-2 100 0.56 0.01 
(Invention) 
1-2 I-9 100 0.56 0.01 
(Invention) 
1-3 I-15 100 0.55 0.01 
(Invention) 
1-4 I-20 100 0.56 0.01 
(Invention) 
1-5 I-27 100 0.56 0.01 
(Invention) 
1-6 I-32 100 0.56 0.01 
(Invention) 
1-7 Comparative 88 0.55 0.03 
(Comparison) 
Dye 1 
1-8 Comparative 80 0.56 0.03 
(Comparison) 
Dye 2 
1-9 -- 100 0.42 0.00 
(Comparison) 
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As is apparent from the results in Table 3 above, all the photographic 
material samples containing the dye of the present invention had a higher 
sharpness with less color retention than the comparative samples and that 
decrease of the sensitivity of the samples of the present invention was 
smaller than that of the comparative samples. 
EXAMPLE 2 
Silver halide photographic material Sample (II-1) was prepared by the 
method described in JP-A-3-249752, from page 24, left top column, line 7 
to page 25, left bottom column, line 20, except that a dispersion of dye 
(I-9) of the present invention, as prepared by the same method as that in 
Example 1, was used in place of dye (I-1) described in JP-A-3-249752, page 
24, left top column, line 18. The amount of dye (I-9) in Sample (II-1) was 
140 mg/m.sup.2. Other photographic material Samples (II-2) to (II-15) were 
prepared in the same manner as above, except that dye (I-9) was replaced 
by the dye as indicated in Table 4 below. 
The samples thus prepared were stored under the condition of 40.degree. C. 
and 80% RH for 3 days and then processed in accordance with the process 
described in JP-A-3-249752, from page 25, right bottom column, line 8 to 
page 26, left top column (table). The fresh samples were also processed in 
the same manner. The difference in the sensitivity between the fresh 
sample and the stored sample was obtained as the degree of 
desensitization. The results obtained are shown in Table 4. 
TABLE 4 
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Degree of 
Sample Dye(*) Desensitization 
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II-1 (Invention) 
I-9 0.03 
II-2 (Invention) 
I-10 0.04 
II-3 (Invention) 
I-11 0.03 
II-4 (Invention) 
I-15 0.04 
II-5 (Invention) 
I-17 0.03 
II-6 (Invention) 
I-20 0.03 
II-7 (Invention) 
I-25 0.04 
II-8 (Invention) 
I-27 0.03 
II-9 (Invention) 
I-30 0.04 
II-10 (Invention) 
I-35 0.03 
II-11 (Invention) 
I-37 0.04 
II-12 (Invention) 
I-38 0.03 
II-13 (Comparison) 
Comparative Dye 1 
0.18 
II-14 (Comparison) 
Comparative Dye 2 
0.16 
II-15 (Comparison) 
-- 0.03 
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(*) The amount added is 140 mg/m.sup.2. 
##STR17## 
As is apparent from the results of Table 4 above, Samples (II-1) to (II-12) 
containing the dye of the present invention had higher storage stability 
than comparative Samples (II-13) and (II-14), as the degree of 
desensitization of the former after storage is smaller than the that of 
the latter. After processing, the comparative Samples (II-13) and (II-14) 
were found to have blue color retention, while Samples (II-1) to (II-12) 
of the present invention had no color retention. Thus, it is understood 
that the decolorability of the dyes of the present invention in the 
processed samples is better than the comparative dyes. In addition, the 
sharpness of all the dye-added Samples (II-1) to (II-14) was better than 
that of the dye-free Sample (II-15). 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.