Method for hardening gelatin and silver halide photographic light sensitive materials employing the method

A method for hardening gelatin comprises the step of mixing gelatin with a compound represented by the following formula (I), (II) or (III): ##STR1## wherein R.sub.1 and R.sub.2 independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group or R.sub.1 and R.sub.2 combine with each other to form a nitrogen-containing heterocyclic ring; J represents an organic group; 1 represents an integer of 2 to 5; and m represents an integer of 1 to 5.

FIELD OF THE INVENTION 
The present invention relates to a method for hardening gelatin and a 
silver halide photographic light-sensitive material using the method, and 
more particularly to a method for hardening gelatin with an improved 
hardener and a silver halide photographic light-sensitive material using 
the method. 
BACKGROUND OF THE INVENTION 
Gelatin is used as a binder of many silver halide photographic 
light-sensitive material. Generally, a silver halide photographic 
light-sensitive material (hereinafter referred to as simply 
light-sensitive material) has a silver halide emulsion layer, an 
intermediate layer, a protective layer, a filter layer, a subbing layer, 
an anti-halation layer, a UV absorbing layer, an anti-static layer or a 
backing layer on a support such as glass, paper, or synthetic resin film. 
These various photographic constitution layers contain gelatin as a main 
component The photographic constitution layers, which are obtained by 
coating an aqueous solution containing a hydrophilic polymer and/or a 
water-dispersible polymer on a support, have a poor mechanical strength. 
For example, a gelatin membrane has lower melting point and extremely 
swells in water. A latex membrane has disadvantages in that its adhesion 
to a support is poor and it is likely to exfoliate. 
It is well known that a compound called "hardener" is added to photographic 
structural layers to enhance mechanical strength thereof. For example, 
organic hardeners including aldehyde compounds such as formaldehyde and 
glutaric aldehyde, compounds having reactive halogen described in U.S. 
Pat. Nos. 2,732,303, 3,288,775, 3,951,940, British Patent Nos. 974,723 and 
1,167,207, ketone compounds such as diacetyl and cyclopentadione, 
bis(2-chloroethyl)urea, 2-hydroxy-4,6-dichloro-1,3,5-triazine, 
divinylsulfone, 5-acetyl-1,3-diacroylhexahydro-1,3,5-triazine, compounds 
having a reactive olefin as described in U.S. Pat. Nos. 3,232,763 and 
3,635,718 and British Patent No. 994,809, vinylsulfonyl compounds 
described in U.S. Pat. Nos. 3,539,644, and 3,642,486, Japanese Publication 
Nos. 49-13563/1974, 53-47271/1978 and 56-48860/1981, and Japanese Patent 
O.P.I. Publication Nos. 53-57257/1978, 61-128240/1986, 62-4275/1987, 
63-53541/1988 and 63-264572/1988, N-hydroxymethylphthalimide, N-methylol 
compounds described in U.S. Pat. Nos. 2,732,316 and 2,586,168, isocyanates 
described in U.S. Pat. No. 3,103,437, azilidine compounds described in 
U.S. Pat. Nos. 2,983,611 and 3,017,280, acid derivatives described in U.S. 
Pat. Nos. 2,725,294 and 2,725,295, carbodiimides in U.S. Pat. No. 
3,100,704, epoxy compounds described in U.S. Pat. No. 3,091,537, 
isooxazoles described in U.S. Pat. Nos. 3,321,313 and 3,543,292, 
halogencarboxylic aldehydes such as mucochlorolic acid, dioxane 
derivatives such as dihydroxydioxane and dichlorodioxane or inorganic 
hardeners including alum chromate, zirconium sulfate and chromium 
trichloride are cited. 
However, the above-mentioned conventional hardeners, when used for a 
photographic light-sensitive material, have some shortcomings in that 
hardening effect is insufficient, there is long-termed change of the 
degree of hardness called after-hardening due to slow hardening effect on 
gelatin, an adverse affect (increase of fogging, reduction of sensitivity 
or maximum density or contrast reduction) on the performance of 
photographic light-sensitive material, loss of hardening effect due to 
other co-existing photographic additives and reduction of the effects of 
other photographic additives (for example, a coupler in 
coupler-in-emulsion type color emulsion). 
As a hardener wherein hardening reaction on gelatin is relatively speedy 
and after-hardening is small, compounds having a dihydroquinoline skeleton 
described in Japanese Patent O.P.I. Publication No. 50-38540/1975, 
N-carbamoyl pyridinium salts described in Japanese Patent O.P.I. 
Publication Nos. 51-59625/1976, 62-262854/1987, 62-264044/1987 and 
63-184741/1988, acylimidazols described in Japanese Patent Publication No. 
55-38655/1980, compounds having 2 or more N-acyloxyimino groups in a 
molecule described in Japanese Patent Publication No. 53-22089/1978, 
compounds having an N-sulfonyloxyimide group described in Japanese Patent 
OPI Publication No. 52-93470/1977, compounds having a phosphor-halogen 
linkage described in Japanese Patent OPI Publication No. 58-113929/1983, 
and chloroformamidium described in Japanese Patent OPI Publication Nos. 
60-225148/1985, 61-240236/1986 and 63-41580/1988 are known. 
Among the above compounds, the N-carbamoylpyridium salts have high 
hardening speed and reduced after-hardening degree. However, an amine, 
which is a by-product produced after hardening reaction, has an adverse 
effect on light sensitive materials to the degree which is not 
disregarded. 
To the contrary, the vinylsulfonyl compounds described above, which do not 
produce the by-product, are known. These compounds have reduced adverse 
effects on the light sensitive materials, but have shortcomings in lower 
hardening speed and low water solubility. 
U.S. Pat. No. 5,411,856 discloses vinylsulfonyl compounds which these 
shortcomings are improved, but hardening speed is not yet satisfactory. 
Accordingly, a hardener which has higher hardening speed has been sought. 
SUMMARY OF THE INVENTION 
A first object of the present invention is to provide a novel gelatin 
hardener with high hardening speed and reduced after-hardening and a 
method of hardening gelatin. A second object of the present invention is 
to provide a silver halide photographic light sensitive material wherein a 
gelatin layer is hardened with the novel hardener with high hardening 
speed and reduced after-hardening without an adverse effect on the 
photographic properties. 
DETAILED DESCRIPTION OF THE INVENTION 
The above-mentioned object on the invention can be attained the following 
constitution: 
(1) A method for hardening gelatin employing at least one of compounds 
represented by the following formulae (I), (II) and (III): 
##STR2## 
wherein R.sub.1 and R.sub.2 independently represent a hydrogen atom, an 
alkyl group, an aryl group or a heterocyclic group or R.sub.1 and R.sub.2 
may combine with each other to form a nitrogen-containing heterocyclic 
ring; J represents an organic group; 1 represents an integer of 2 to 5; 
and m represents an integer of 1 to 5, 
(2) the method for hardening gelatin of (1) above, wherein said J 
represents an alkylene group which may have another organic group in the 
alkylene chain, 
(3) A method for hardening gelatin employing at least one of compounds 
represented by the following formulae (IV), (V) and (VI): 
##STR3## 
wherein R.sub.1 and R.sub.2 independently represent a hydrogen atom, an 
alkyl group, an aryl group or a heterocyclic group or R.sub.1 and R.sub.2 
may combine with each other to form a nitrogen-containing heterocyclic 
ring; R.sub.3 represents a hydrogen atom or a substituent; R.sub.4 
represents an alkylene group; and n represents an integer of 0 or 1, 
(4) A silver halide photographic light sensitive material comprising a 
support and provided thereon, at least one hydrophilic colloid layer, 
wherein said at least one hydrophilic colloid layer is hardened with at 
least one of compounds represented by the above formulae (I), (II) and 
(III), 
(5) The method for hardening gelatin of (4) above, wherein said J 
represents an alkylene group which may have another organic group in the 
alkylene chain, or 
(6) A silver halide photographic light sensitive material comprising a 
support and provided thereon, at least one hydrophilic colloid layer, 
wherein said at least one hydrophilic colloid layer is hardened with at 
least one of compounds represented by the above formulae (IV), (V) and 
(VI). 
The invention will be detailed below. 
The compound of the invention represented by formula (I), (II) or (III) 
will be explained below. 
In formula (I), (II) or (III), R.sub.1 and R.sub.2 independently represent 
a hydrogen atom, a straight-chained or brached alkyl group (for example, 
methyl, ethyl, i-propyl or cyclohexyl), an aryl group (for example, 
phenyl) or a heterocyclic group (for example, morpholino or pyridyl) or 
R.sub.1 and R.sub.2 may combine with each other to form a 
nitrogen-containing heterocyclic ring (for example, morpholino or 
piperino). The group other than a hydrogen atom represented by R.sub.1 and 
R.sub.2 may have a substituent. The substituent represents the same as 
those in R.sup.3 denoted later. 
J represents an organic group such as alkylene, phenylene or heterocyclic, 
and the group may have a substituent. 
The substituent represents the same as those of R.sub.3 denoted later. J 
preferably represents an alkylene group or an alkylene group having 
another organic divalent group in the alkylene main chain. The alkylene 
group having another organic divalent group is an alkylene group having, 
in the alkylene main chain, at least one of --O--, --S--, --(C.dbd.O)--, 
--SO.sub.2 --, --(C.dbd.O)NR-- and --NR-- in which R represents hydrogen 
or alkyl. 
1 represents 2 to 5, preferably 2 to 4, and more preferably 2. m represents 
1 to 5, preferably 1 to 4, and more preferably 1 or 2. 
The compound of the invention represented by formula (IV), (V) or (VI) will 
be explained below. 
In formula (IV), (V) or (VI), R.sub.1 and R.sub.2 represent the same as 
R.sub.1 and R.sub.1 denoted above in formula (I), (II) or (III). 
R.sub.3 represents a hydrogen atom or a substituent, the substituent 
includes the following: 
an alkyl group (for example, methyl, ethyl, propyl,iso-propyl, tert-butyl, 
pentyl, cyclopentyl, hexyl or cyclohexyl); an alkenyl group (for example, 
vinyl or allyl); an alkinyl group (for example, propagyl); an aryl group 
(for example, phenyl); a heterocyclic ring group (for example, pyridyl, 
thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pirazinyl, pyrimidyo, 
pyridazinyl, selenazolyl, sulforanyl, piprdidinyl, pyrazolyl or 
tetrazolyl); a halogen atom (for example, a chlorine, bromine iodine or 
fluorine atom); an alkoxy group (for example, methoxy, ethoxy, propyloxy, 
pentyloxy, cyclopentyloxy, hexyloxy or cyclohexyloxy); an aryloxy group 
(for example, phenoxy); an alkoxycarbonyl group (for example, 
methyloxycarbonyl, ethyloxycarbonyl or butyloxycarbonyl); an 
aryloxycarbonyl group (for example, phenoxycarbonyl); a sulfonylamino 
group (for example, methylsulfonylamino, ethylsulfonylamino, 
butylsulfonylamino, hexylsulfonylamino, cyclohexylsulfonylamino or 
phenylsulfonylamino); a sulfamoyl group (for example, aminosulfonyl, 
methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, 
hexylaminosulfonyl, cyclohexylaminosulfonyl, phenylaminosulfonyl or 
2-pyridylaminosulfonyl); a ureido group (for example, methylureido, 
ethylureido, penylureido, hexylureido, cyclohexylureido, phenylureido or 
2-pyridylureido); an acyl group (for example, an acetyl, ethylcarbonyl, 
propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, phenylcarbonyl or 
pyridylcarbonyl; a carbamoyl group (for example, aminocarbonyl, 
methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, 
pentylaminocarbonyl, cyclohexylaminocarbonyl, phenylaminocarbonyl or 
2-pyridylaminocarbonyl); an amide group (for example, methylcarbonylamino, 
ethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino or 
phenylcarbonylamino); a sulfonyl group (for example, methylsulfonyl, 
ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, phenylsulfonyl or 
2-pyridylsulfonyl group); an amino group (for example, amino, ethylamino, 
dimethylamino, butylamino, cyclopentylamino, anilino or 2-pyridylamino); a 
cyano group; a nitro group; a sulfo group; a carboxy group; a hydroxy 
group or an oxamoyl group. 
The substituent represented by R.sub.3 is preferably an alkyl group, an 
aryl group, a heterocyclic group, a carboxy group, an alkoxycarbonyl 
group, aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a 
cyano group, an oxamoyl group, a hydroxy group, an alkoxy group, an acyl 
group, a sulfo group or a halogen atom. 
The substituent represented by R.sub.4 represents an alkylene group such as 
methylene, ethylene, trimethylene, tetramethylene or propylene, each of 
which may have a substituent. 
The substituent of the group other than a hydrogen atom represented by 
R.sub.1 and R.sub.2, the organic group represented by J or the alkylene 
group represented by R.sub.4 is the same as that denoted above in R.sub.3. 
The exemplified compound of a compound represented by formula (I), (II) or 
(III) in the invention will be shown below, but the invention is not 
limited thereto. 
##STR4## 
The synthetic method of the compound of the invention will be shown below. 
Of compounds represented by formula (I), Compound I-1 can be synthesized 
according to the following routes: 
##STR5## 
The compound can be also synthesized according to following route. 
##STR6## 
The compound can be also synthesized according to following route. 
##STR7## 
The compound can be also synthesized according to following route. 
##STR8## 
Compound I-3 can be synthesized using Cl.sub.2 CHSO.sub.2 N(CH.sub.3).sub.2 
or Cl.sub.2 CHSO.sub.3 CH.sub.3 in the same manner as the routes (routes 
A, B, C and D) in I-1 above, but can be also synthesized according to 
following route. 
##STR9## 
Compound I-4 can be synthesized in the same manner as the routes (routes A, 
B, C and D) in I-1 above, but can be also synthesized according to 
following route. 
##STR10## 
Compound I-4 can also be synthesized according to the following route. 
##STR11## 
The compound can be also synthesized according to following route. 
##STR12## 
The other compound represented by Formula (I) can be also synthesized in 
the same manner as above. 
For example, Compound I-7 can be synthesized using CH.sub.3 C(Cl).sub.2 
SO.sub.2 NH.sub.2 in the same manner as route A or B or using CH.sub.3 
C(Cl).sub.2 SO.sub.3 CH.sub.3 in the same manner as route C or D. The 
compound can be also synthesized by alkylation of Compound I-1 as a 
starting compound with CH.sub.3 I. 
Compound I-10 can be synthesized in the same manner as route H, using 
ClCH.sub.2 SO.sub.2 NH.sub.2 and Compound I-4 as a starting compound or in 
the same manner as route F, G or H using two times mole of ClCH.sub.2 
SO.sub.2 NH.sub.2 or ClCH.sub.2 SO.sub.3 CH.sub.3. 
Of compounds of Formula (II), Compound II-1 can be synthesized in the same 
manner as the above routes (routes A, B, C and D) in above I-1 using 
Cl.sub.2 CHCOCONH.sub.2 or Cl.sub.2 CHCOCOOCH.sub.3. 
Compound II-3 can be synthesized in the same manner as the routes (routes 
A, B, C and D) in above II-1 using Cl.sub.2 CHCOCON(CH.sub.3).sub.2 or 
Cl.sub.2 CHCOCOOCH.sub.3, but can be also synthesized according to the 
following route. 
##STR13## 
Compound II-4 can be synthesized in the same manner as the routes (routes 
A, B, C and D) in above II-1, but can be also synthesized in the same 
manner as the routes (routes F, G and H) in Compound I-4 using ClCH.sub.2 
COCONH.sub.2 or ClCH.sub.2 COCOOCH.sub.3. 
II-4 can be also synthesized according to the following route. 
##STR14## 
II-4 can be also synthesized according to the following route. 
##STR15## 
The other compound represented by Formula (II) can be also synthesized in 
the same manner as above. 
For example, Compound II-7 can be synthesized in the same manner as route A 
or B, using CH.sub.3 C(Cl).sub.2 COCONH.sub.2 as a starting material or in 
the same manner as route C or D using CH.sub.3 C(Cl).sub.2 COCOOCH.sub.3 
as a starting material. The compound can be also synthesized by alkylation 
of Compound II-1 as a starting compound with CH.sub.3 I. 
Compound II-10 can be synthesized in the same manner as route H, using 
ClCH.sub.2 COCONH.sub.2 and Compound II-4 as a starting compound or in the 
same manner as route F, G or H using two times mole of ClCH.sub.2 
COCONH.sub.2 or ClCH.sub.2 COOCH.sub.3. 
Of compounds of Formula (III), Compound III-1 can be synthesized in the 
same manner as the above routes (routes A and B) in above I-1 using 
Cl.sub.2 CHCN, but can be also synthesized according to the following 
route. 
##STR16## 
Compound III-2 can be synthesized in the similar manner as the routes 
(routes A and B) in above III-1, but can be also synthesized in the same 
manner as the routes (routes F and G) in Compound I-4 using Cl.sub.2 CHCN 
as a starting material. 
Compound III-4 can be also synthesized according to the following route. 
##STR17## 
Compound III-4 can be also synthesized according to the following route. 
##STR18## 
The compound can be also synthesized by alkylation of Compound III-1 as a 
starting compound with CH.sub.3 I. 
The other compound represented by Formula (III) can be also synthesized in 
the same manner as above. 
For example, Compound III-6 can be synthesized in the same manner as route 
H using Cl.sub.2 CHCN and III-2 as a starting material or in the same 
manner as route F or H using two times mole of Cl.sub.2 CHCN. 
Compounds of Formula (III) having a cyano group can be obtained by 
dehydrating the corresponding carbamoyl compounds with phosphorus 
oxychloride. The corresponding carbamoyl compounds can be synthesized in 
the same manner as routes A through N in the invention, using Cl.sub.2 
CHCONH.sub.2, Cl.sub.2 CHCOOCH.sub.3, Cl.sub.2 CHCON(CH.sub.3).sub.2, 
ClCON(CH.sub.3).sub.2, ClCH.sub.2 CONH.sub.2, ClCH.sub.2, COOCH.sub.3 or 
HC.tbd.C--COOCH.sub.3 as a starting material. The corresponding carbamoyl 
compounds can be synthesized according to a method disclosed in U.S. Pat. 
No. 5,411,856. 
These compounds are dissolved in water or a hydrophilic solvent such as 
methanol and ethanol, and then, added to a photographic coating solution. 
A gelatin layer forming a hydrophilic colloid layer is a photographic 
structural layer containing gelatin such as a light-sensitive or 
non-sensitive silver halide emulsion layer, a protective layer, an 
intermediate layer, a filter layer, an anti-static layer, a development 
adjusting layer, a subbing layer, an anti-halation layer and a backing 
layer. The addition amount of the compound in the invention represented by 
Formula (I), (II) or (III) in the above-mentioned layer is not the same 
depending upon the kind of a compound or a coating solution. It is 
desirably 0.01 to 2.0 mmol and more desirably 0.03 to 1.0 mmol per 1 g of 
the total gelatin weight on one side of a support. Gelatin molecules are 
cross-linked by the compound in the invention, whereby gelatin is 
hardened. 
The compound represented by the above-mentioned Formula (I), (II) or (III) 
in the present invention may be combined with other conventional hardeners 
to be used. Practical examples of conventional hardener combined to be 
used include aldehyde type compounds such as formaline, glyoxal and 
succinic aldehyde, acid-releasing triazine compounds described in Japanese 
Patent Publication No. 6151/1972 including sodium 
2,4-dichloro-6-hydroxytriazine or carbamoyl pyridium compounds. 
The silver halide grains used in the present invention are preferably 
ordinary crystal grains (including a cubic, octahedral and 
tetradecahedral) and more preferably tabular grains. The average grain 
size of silver halide grains is preferably 0.2 to 2.5 .mu.m, and more 
preferably 0.4 to 2.0 .mu.m. 
The average value (referred to as the average aspect ratio) of grain 
diameter/thickness (referred to as the aspect ratio) in the tabular silver 
halide grains of the present invention is 3 or more, preferably 3 to 30, 
more preferably 3 to 20 and most preferably 3 to 10. 
The average thickness of the tabular silver halide grains of the present 
invention is preferably 0.4 .mu.m or less, more preferably 0.3 .mu.m or 
less and most preferably 0.05 to 0.25 .mu.m. 
In the present invention, the diameter of silver halide grains is defined 
to be diameter of a circle having an area equivalent to the projected area 
of grains through observation of an electron microscopic photographic of a 
silver halide grain. 
In the present invention, the thickness of silver halide grains is defined 
to be the minimum distance between two parallel planes constituting 
tabular silver halide grains. The thickness of tabular silver halide 
grains can be calculated by means of an electron microscopic photography 
provided with shadow of silver halide grains or an electron microscopic 
photography of the dislocation of a sample wherein a silver halide 
emulsion is coated on a support to be dried. 
In order to calculate the average aspect ratio, at least 100 samples are 
measured. 
In the silver halide emulsion in the present invention, a ratio of tabular 
silver halide grains to the total silver halide grains is preferably 50% 
or more, more preferably 60% or more and most preferably 70% or more. 
The tabular silver halide emulsion in the present invention is preferably 
mono-dispersed. Silver halide grains whose grain size is included in 
.+-.20% of the average grain size are preferably 50 wt % or more. In 
addition, it is also desirable to mix mono-dispersed grains to use. In 
such an instance, the grain size distribution of grains in the 
light-sensitive material has two or more maximum values. 
In the tabular silver halide emulsion of the present invention, any of 
halogen composition such as silver chloride, silver bromide, silver 
iodochloride, silver bromochloride, silver bromoiodide and silver 
bromochloroiodide may be used. In terms of high sensitivity, silver 
bromochloroiodide is preferable. The average silver iodide content is 0 to 
4.0 mol % and preferably 0.2 to 3.0 mol %. The average silver chloride 
content is 0 to 5 mol %. In the tabular silver halide emulsion in the 
present invention, the halogen composition may be uniform or silver iodide 
may be localized in a grain, and one wherein silver iodide is localized in 
the central portion is preferably used. 
For a production method of the tabular silver halide emulsion, it is 
possible to refer to Japanese Patent OPI Publication Nos. 113926/1983, 
113927/1983, 113934/1983 and 1855/1987 and European Patent Nos. 219,849 
and 219,850. 
For a production method of a mono-dispersed tabular silver halide emulsion, 
it is possible to refer to Japanese Patent OPI Publication No. 6643/1986. 
A tabular silver bromoiodide emulsion having high aspect ratio can be 
produced in a method wherein an aqueous gelatin solution whose pBr is kept 
at 2 or lower, an aqueous silver nitrate solution is added or an aqueous 
silver and an aqueous halogenized solution are added concurrently to 
create seed crystals, and then, grow them by means of a double jet method. 
Size of a tabular silver halide grain can be controlled by temperature 
during formation of grains and by addition speed of silver salt and an 
aqueous halogenated solution. 
The average silver iodide content of the tabular silver halide emulsion can 
be controlled by changing the composition of an aqueous halogenated 
substance added, i.e., the ratio between a bromide and a iodide. 
In producing tabular silver halide grains, a silver halide solvent such as 
ammonia, thioether and thiourea can be used. 
In order to remove a soluble salt from an emulsion, a water-washing methods 
such as a noodle water-washing method and a flocculation precipitation 
method are allowed to be used. As a desirable water-washing method, a 
method that uses an aromatic hydrocarbon aldehyde resin containing a sulfo 
group described in Japanese Patent OPI Publication No. 16086/1960 is 
cited. In addition, as a desirable desalting method, a method that uses 
illustrated coagulation polymers G-3 and G-8 described in Japanese Patent 
OPI Publication No. 7037/1990 is cited. 
An emulsion used for the photographic coating solution of the present 
invention can be produced by a conventional method. For example, methods 
described in 1. Emulsion Preparation and types in Research Disclosure (RD) 
No. 17643 (December, 1978), pp. 22 to 23 and RD. No. 18716 (November, 
1979), on page 648 can be used. 
The emulsion used for the photographic coating solution of the present 
invention can be prepared by methods described in "The Theory of the 
Photographic Process" 4th Edition (1977), written by T. H. James, 
published by Macmillan Inc., on pp. 38 to 104, "Photographic Emulsion 
Chemistry" (1966) written by G. F. Dauffin, published by Focal Press Inc., 
"Chimie et Physique Photographique" written by P. Glafkides, published by 
Paul Montel (1967) and "Making and Coating Photographic Emulsion" written 
by V. L. Zelikman and others, published by Focal Press Inc. (1964). 
Namely, under a solution condition of a neutral method, an acid method and 
an ammonia method, a mixing condition of an ordinary mixing method, a 
reverse mixing method, a double jet method and a controlled double jet 
method and a grain preparation condition of a conversion method and a 
core/shell method and their mixture can be selected for producing the 
emulsion. One of desirable embodiments of the present invention is a 
mono-dispersed emulsion wherein silver iodides are localized inside each 
grain. 
The silver halides, chemical sensitizers, silver halide solvents, spectral 
sensitizing dyes, anti-foggants, hydrophilic protective colloids such as 
gelatin, UV absorbers, polymer latexes, brightening agents, color 
couplers, anti-fading agents, dyes, matting agents or surfactants, which 
are used in a silver halide emulsion layer or other layers of the light 
sensitive materials used in the invention, are used without any 
limitation. 
To the emulsion used in the silver halide photographic light sensitive 
material of the present invention, various photographic additives can be 
added during a physical ripening step or before or after a chemical 
ripening step. As conventional additives, for example, compounds described 
in Research Disclosure Nos. 17643, 18716 (November, 1979) and 308119 
(December, 1989) are cited. Kind of compound and place described in these 
three RDs are illustrated as follows: 
______________________________________ 
RD-17643 RD-18716 RD-308119 
Classifi- Classifi- Classifi- 
Additive Page cation Page cation 
Page cation 
______________________________________ 
Chemical 23 III 648 996 III 
sensitizer upper 
right 
Sensitizing 
23 IV 648- 996-8 
IVA 
dye 649 
Desensitizing 
23 IV 998 IVB 
dye 
Pigment 25-26 VIII 649- 1003 VIII 
650 
Development 
29 XXI 648 
accelerator upper 
right 
Anti-foggant 
24 IV 649 1006-7 
VI 
and stabilizer upper 
right 
Brightening 
24 V 998 V 
agent 
Surfactant 
26-7 XI 650 1005-6 
XI 
right 
Anti-static 
27 XII 650 1006-7 
XIII 
agent right 
Plasticizer 
27 XII 650 1006 XII 
right 
Lubricant 
27 XII 
Matting agent 
28 XVI 650 1008-9 
XVI 
right 
Binder 26 XXII 1003-4 
IX 
Support 28 XVII 1009 XVII 
______________________________________ 
As a support capable of being used in the light-sensitive material of the 
present invention, those described in the above-mentioned RD-17643, page 
28 and RD-308119, page 1009 are cited 
As a suitable support, a plastic film is cited. On the surface of such a 
support, a subbing layer, corona discharge for UV irradiation may be 
provided for the better adhesion of coating layer. 
The photographic coating solution wherein the present invention can be 
applied are used for a direct x-ray film, an indirect X-ray film, an X-ray 
reversal film for duplicating use, a film for a CT imager, a film for a 
laser imager, a graveur film for graphic arts, a line image film for 
graphic arts, a dot-photographing film for graphic arts, a 
contact-printing film for graphic arts, a black-and-white film for 
photography and a color film for photography. 
A light-sensitive material formed by the use of the photographic coating 
solution of the present invention can be subjected to photographic 
processing by means of a conventional method. For example, various methods 
and various processing solutions described in Research Disclosure No. 
17643 can be used.

EXAMPLES 
The invention will be detailed according to the following examples, but it 
is not limited thereto. 
Example 1 
The following layer compositions were sequentially formed on a triacetyl 
cellulose film support having a subbing layer in the order from the 
support side to yield multi-layered color photographic light-sensitive 
material samples, I-A through I-E, II-A through II-E, III-A through III-E 
and IV-A. 
The addition amount of compounds in silver halide photographic 
light-sensitive material is expressed in gram per m.sup.2, unless 
otherwise stated. The amount for silver halide and colloidal silver is 
converted to the amounts of silver, and the amount of sensitizing dyes are 
shown in mol per mol of silver. 
______________________________________ 
Layer 1: Antihalation layer 
Black colloidal silver 0.16 
UV absorbent (UV-1) 0.20 
High boiling solvent (Oil-1) 
0.12 
Gelatin 1.53 
Layer 2: Intermediate layer 
Antistaining agent (SC-1) 0.06 
High boiling solvent (Oil-2) 
0.08 
Gelatin 0.80 
Layer 3: Low speed red-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
0.43 
size 0.38 .mu.m, Silver iodide content 8.0 mol %) 
Silver iodobromide emulsion (Average grain 
0.15 
size 0.27 .mu.m, Silver iodide content 2.0 mol %) 
Sensitizing dye (SD-1) 2.8 .times. 10.sup.-4 
Sensitizing dye (SD-2) 1.9 .times. 10.sup.-4 
Sensitizing dye (SD-3) 1.9 .times. 10.sup.-4 
Sensitizing dye (SD-4) 1.0 .times. 10.sup.-4 
Cyan coupler (C-1) 0.56 
Colored cyan coupler (CC-1) 
0.021 
DIR compound (D-1) 0.025 
High boiling solvent (Oil-1) 
0.49 
Gelatin 1.14 
Layer 4: Medium speed red-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
0.89 
size 0.52 .mu.m, Silver iodide content 8.0 mol %) 
Silver iodobromide emulsion (Average grain 
0.22 
size 0.38 .mu.m, Silver iodide content 8.0 mol %) 
Sensitizing dye (SD-1) 2.3 .times. 10.sup.-4 
Sensitizing dye (SD-2) 1.2 .times. 10.sup.-4 
Sensitizing dye (SD-3) 1.6 .times. 10.sup.-4 
Cyan coupler (C-1) 0.45 
Colored cyan coupler (CC-1) 
0.038 
DIR compound (D-1) 0.017 
High boiling solvent (Oil-1) 
0.39 
Gelatin 1.01 
Layer 5: High speed red-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
1.27 
size 1.00 .mu.m, Silver iodide content 8.0 mol %) 
Sensitizing dye (SD-1) 1.3 .times. 10.sup.-4 
Sensitizing dye (SD-2) 1.3 .times. 10.sup.-4 
Sensitizing dye (SD-3) 1.6 .times. 10.sup.-4 
Cyan coupler (C-2) 0.20 
Colored cyan coupler (CC-1) 
0.034 
DIR compound (D-3) 0.001 
High boiling solvent (Oil-1) 
0.57 
Gelatin 1.10 
Layer 6: Intermediate layer 
Antistaining agent (SC-1) 0.075 
High boiling solvent (Oil-2) 
0.095 
Gelatin 1.00 
Layer 7: Intermediate layer 
Gelatin 0.45 
Layer 8: Low speed green-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
0.64 
size 0.38 .mu.m, Silver iodide content 8.0 mol %) 
Silver iodobromide emulsion (Average grain 
0.21 
size 0.27 .mu.m, Silver iodide content 2.0 mol %) 
Sensitizing dye (SD-4) 7.4 .times. 10.sup.-4 
Sensitizing dye (SD-5) 6.6 .times. 10.sup.-4 
Magenta coupler (M-1) 0.19 
Magenta coupler (M-2) 0.49 
Colored magenta coupler (CM-1) 
0.12 
High boiling solvent (Oil-2) 
0.81 
Gelatin 1.89 
Layer 9: Medium speed green-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
0.76 
size 0.59 .mu.m, Silver iodide content 8.0 mol %) 
Sensitizing dye (SD-6) 1.5 .times. 10.sup.-4 
Sensitizing dye (SD-7) 1.6 .times. 10.sup.-4 
Sensitizing dye (SD-8) 1.5 .times. 10.sup.-4 
Magenta coupler (M-1) 0.043 
Magenta coupler (M-2) 0.10 
Colored magenta coupler (CM-2) 
0.039 
DIR compound (D-2) 0.021 
DIR compound (D-3) 0.002 
High boiling solvent (Oil-2) 
0.37 
Gelatin 0.76 
Layer 10: High speed green-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
1.46 
size 1.00 .mu.m, Silver iodide content 8.0 mol %) 
Sensitizing dye (SD-6) 0.93 .times. 10.sup.-4 
Sensitizing dye (SD-7) 0.97 .times. 10.sup.-4 
Sensitizing dye (SD-8) 0.93 .times. 10.sup.-4 
Magenta coupler (M-1) 0.08 
Magenta coupler (M-2) 0.133 
Colored magenta coupler (CM-2) 
0.014 
High boiling solvent (Oil-1) 
0.15 
High boiling solvent (Oil-2) 
0.42 
Gelatin 1.08 
Layer 11: Yellow filter layer 
Yellow colloidal silver 0.07 
Antistaining agent (SC-1) 0.18 
Formalin scavenger (HS-1) 0.14 
High boiling solvent (Oil-2) 
0.21 
Gelatin 0.73 
Layer 12: Intermediate layer 
Formalin scavenger (HS-1) 0.18 
Gelatin 0.60 
Layer 13: Low speed blue-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
0.073 
size 0.59 .mu.m, Silver iodide content 8.0 mol %) 
Silver iodobromide emulsion (Average grain 
0.16 
size 0.38 .mu.m, Silver iodide content 3.0 mol %) 
Silver iodobromide emulsion (Average grain 
0.20 
size 0.27 .mu.m, Silver iodide content 2.0 mol %) 
Sensitizing dye (SD-9) 2.1 .times. 10.sup.-4 
Sensitizing dye (SD-10) 2.8 .times. 10.sup.-4 
Yellow coupler (Y-1) 0.89 
DIR compound (D-4) 0.008 
High boiling solvent (Oil-2) 
0.37 
Gelatin 1.51 
Layer 14: High speed blue-sensitive emulsion layer 
Silver iodobromide emulsion (Average grain 
0.95 
size 1.00 .mu.m, Silver iodide content 8.0 mol %) 
Sensitizing dye (SD-9) 7.3 .times. 10.sup.-4 
Sensitizing dye (SD-10) 2.8 .times. 10.sup.-4 
Yellow coupler (Y-1) 0.16 
High boiling solvent (Oil-2) 
0.093 
Gelatin 0.80 
Layer 15: First protective layer 
Silver iodobromide emulsion (Average grain 
0.30 
size 0.05 .mu.m, Silver iodide content 3.0 mol %) 
UV absorbent (UV-1) 0.094 
UV absorbent (UV-2) 0.10 
Formalin scavenger (HS-1) 0.38 
High boiling solvent (Oil-1) 
0.10 
Gelatin 1.44 
Layer 16: Second protective layer 
Alkali-soluble matting agent (Average grain 
0.15 
size of 2 .mu.m) 
Polymethyl methacrylate (Average grain 
0.04 
size of 3 .mu.m) 
Lubricant (WAX-1) 0.02 
Gelatin 0.55 
______________________________________ 
In addition to the above compounds, a coating aid SU-1, a dispersing agent 
SU-2, a viscosity controlling agent, a stabilizer ST-1, dyes AI-1 and 
AI-2, an antifogging agent AF-1, a stabilizing agent ST-1, 
polyvinylpyrrolidone having a weight average molecular weight of 10,000, 
polyvinylpyrrolidone having a weight average molecular weight of 100,000 
and antseptic agent DI-1 were added. The addition amount of DI-1 was 9.4 
mg/m.sup.2. 
Inventive hardeners and comparative hardener were added to the second 
protective layer immediately before coating. The addition amount of the 
hardeners is an amount based on the total gelatin amount (the sum of 
gelatin added to the first layer through the sixteenth second layer) which 
is shown in Table 2. 
The chemical structures of the compounds used in the above layers are shown 
below. 
##STR19## 
The above obtained samples were fresh samples, and the samples were further 
stored at 50.degree. C. and 50% RH for three days. These samples were 
wedge exposed to a white light and processed according to the following 
processing steps, and sensitivity and fog were measured. 
Sensitivity was represented by a reciprocal of exposure necessary to give a 
density of fog plus 0.5, and sensitivity of samples was represented in 
terms of sensitivity relative to sensitivity of Sample No. I-A stored at 
50.degree. C. and 50% RH for three days after coating being defined as 
100. 
Separate portions of the fresh samples were stored at 50.degree. C. and 50% 
RH for 3 hours, 2 days and 3 days, and each portion was then immersed in 
30.degree. C. water for 5 minutes. A sapphire needle having a radius of 
0.3 mm was brought into pressure contact with the surface of the resulting 
three samples and moved at a rate of 2 mm/second while applying load 
continuously varying from 0 to 200 g. Thus, the load at which the surface 
of the samples was first damaged was designated as surface strength. 
The above results are collectively shown in Table 2. 
______________________________________ 
(Processing Steps) 
Processing Replenishing 
Processing Step 
Processing Time 
Temperature 
Amount* 
______________________________________ 
Color developing 
3 min. 15 sec. 38 .+-. 0.3.degree. C. 
780 ml 
Bleaching 45 sec. 38 .+-. 2.0.degree. C. 
150 ml 
Fixing 1 min. 30 sec. 38 .+-. 2.0.degree. C. 
830 ml 
Stabilizing 60 sec. 38 .+-. 5.0.degree. C. 
830 ml 
Drying 60 sec. 55 .+-. 5.0.degree. C. 
-- 
______________________________________ 
*Replenishing amount is an amount per m.sup.2 of light sensitive material 
processed. 
The processing solutions and replenishing solutions are prepared according 
to the following. 
______________________________________ 
&lt;Preparation of processing solutions&gt; 
(Color Developing solution) 
______________________________________ 
Water 800 ml 
Potassium carbonate 30 g 
Sodium hydrogencarbonate 
2.5 g 
Potassium sulfite 3.0 g 
Sodium bromide 1.3 g 
Potassium iodide 1.2 mg 
Hydroxylamine sulfate 2.5 g 
Sodium chloride 0.6 g 
4-amino-3-methyl-N-ethyl-N-(b- 
4.5 g 
hydroxyethyl)aniline sulfate 
Diethylene triamine pentaacetic 
3.0 g 
acid 
Potassium hydroxide 1.2 g 
______________________________________ 
Water was added to make 1.0 liter, and the developing solution was 
regulated to pH 10.06 by the use of potassium hydroxide or a 20% surfuric 
acid solution. 
______________________________________ 
(Color developing replenishing solution) 
______________________________________ 
Water 800 ml 
Potassium carbonate 35 g 
Sodium hydrogencarbonate 
3.0 g 
Potassium sulfite 5.0 g 
Sodium bromide 0.4 g 
Hydroxylamine sulfate 3.1 g 
4-amino-3-methyl-N-ethyl-N-(b- 
hydroxyethyl)aniline sulfate 
6.3 g 
Diethylene triamine pentaacetic 
3.0 g 
acid 
Potassium hydroxide 2.0 g 
______________________________________ 
Water was added to make 1.0 liter, and the replenishing developing solution 
was regulated to pH 10.18 by the use of potassium hydroxide or a 20% 
surfuric acid solution. 
______________________________________ 
(Bleaching solution) 
______________________________________ 
Water 700 ml 
Ferric (III) ammonium of 1,3-diaminopropane 
125 g 
tetraacetic acid 
Ethylenediamine tetraacetic acid 
2 g 
Sodium nitrate 40 g 
Ammonium bromide 150 g 
Glacial acetic acid 40 g 
______________________________________ 
Water was added to make 1.0 liter, and the bleaching solution was regulated 
to pH 4.4 by the use of aqueous ammonia or glacial acetic acid. 
______________________________________ 
(Bleaching replenishing solution) 
______________________________________ 
Water 700 ml 
Ferric (III) ammonium of 1,3-diaminopropane 
175 g 
tetraacetic acid 
Ethylenediamine tetaacetic acid 
2 g 
Sodium nitrate 50 g 
Ammonium bromide 200 g 
Glacial acetic acid 56 g 
______________________________________ 
Water was added to make 1 liter, and the replenishing bleaching solution 
was regulated to pH 4.0 by the use of aqueous ammonia or glacial acetic 
acid. 
______________________________________ 
Fixing solution) 
______________________________________ 
Water 800 ml 
Ammonium thiocyanate 120 g 
Ammonium thiosulfate 150 g 
Sodium sulfite 15 g 
Ethylenediamine tetraacetic acid 
2 g 
______________________________________ 
Water was added to make 1 liter, and the fixing solution was regulated to 
pH 6.2 by the use of aqueous ammonia or glacial acetic acid. 
______________________________________ 
(Fixing replenishing solution) 
______________________________________ 
Water 800 ml 
Ammonium thiocyanate 150 g 
Ammonium thiosulfate 180 g 
Sodium sulfite 20 g 
Ethylenediamine tetraacetic acid 
2 g 
______________________________________ 
Water was added to make 1 liter, and the replenishing solution to pH 6.5 by 
the use of aqueous ammonia or glacial acetic acid. 
______________________________________ 
Stabilizing solution and stabilizing replenishing solution) 
______________________________________ 
Water 900 ml 
p-Octylphenol ethyleneoxide (10 mol) adduct 
2.0 g 
Dimethylol urea 0.5 g 
Hexamethylene tetraamine 0.2 g 
1,2-benzisothiazoline-3-on 
0.1 g 
Siloxane (L-77 produced by UCC) 
0.1 g 
Aqueous ammonia 0.5 ml 
______________________________________ 
Water was added to make 1.0 liter, and pH was regulated to 8.5 by the use 
of aqueous ammonia or a 50% sulfuric acid solution. 
TABLE 2 
__________________________________________________________________________ 
Photographic 
Hardener properties 
Addition 
Forced aging 
amount 
conditions 
mmol/100 g 
3 days Hardening property 
Sample of (50.degree. C., 50% RH) 
Surface strength (g) 
No. Kinds gelatin 
Sensitivity 
Fog 
3 hrs 
2 days 
3 days 
__________________________________________________________________________ 
I-A I-4 10 100 0.07 
120 130 130 
(INV.) 
I-B I-5 10 99 0.07 
125 133 133 
(INV.) 
I-C I-7 10 101 0.07 
118 128 128 
(INV.) 
I-D I-8 10 99 0.07 
115 132 132 
(INV.) 
I-E I-11 10 99 0.07 
123 130 130 
(INV.) 
II-A II-4 10 100 0.07 
120 129 129 
(INV.) 
II-B II-5 10 98 0.07 
124 133 133 
(INV.) 
II-C II-7 10 101 0.07 
125 131 131 
(INV.) 
II-D II-8 10 99 0.07 
122 132 132 
(INV.) 
II-E II-11 10 98 0.07 
120 130 130 
(INV.) 
III-A 
III-2 10 100 0.07 
117 127 127 
(INV.) 
III-B 
III-3 10 100 0.07 
122 133 133 
(INV.) 
III-C 
III-4 10 99 0.07 
119 129 129 
(INV.) 
III-D 
III-5 10 99 0.07 
120 130 130 
(INV.) 
III-E 
III-7 10 100 0.07 
122 131 131 
(INV.) 
IV-A Comparative 
10 96 0.09 
100 105 110 
(Comp.) 
compound (1) 
__________________________________________________________________________ 
##STR20## 
(compound disclosed in U.S. Pat. No. 5,411,856) 
As is apparent from Table 2, Samples I-A through I-E, II-A through II-E and 
III-A through III-E, which employ the hardener of the invention, minimize 
fog increase and relative sensitivity lowering under the forced aging 
conditions. Accordingly, the hardener of the invention has no adverse 
affect on the photographic properties. As is also seen from the test 
results of the hardening property, the surface strength of Samples I-A 
through I-E, II-A through II-E and III-A through III-E does not vary after 
the two day or more storage, but Comparative sample IV-B does. 
Accordingly, the hardener of the invention has no after-hardening 
property. 
Example 2 
(Preparation of Seed emulsion-I) 
Seed emulsion-I was prepared by the following method. 
______________________________________ 
Solution A1 
Ossein gelatin 24.2 g 
Distilled water 9657 ml 
Propyleneoxy-polyethyleneoxy-discuccinate 
6.78 ml 
sodium salt (10% ethanol solution) 
KBr 10.8 g 
10% nitric acid 114 ml 
Solution B1 
2.5N aqueous AgNO.sub.3 solution 
2825 ml 
Solution C1 
KBr 841 g 
Water was added to make 2825 ml. 
Solution D1 
1.75N aqueous KBr solution 
an amount for 
controlling the 
following silver 
potential 
______________________________________ 
By the use of a mixing stirrer described in Japanese Patent Publication 
Nos. 58288/1983 and 58289/1982, 464.3 ml of each of Solution B1 and 
Solution C1 were added to Solution A1 in 1.5 minutes at 42.degree. C. by a 
double-jet method to form a nuclei. 
After addition of Solutions B 1 and C 1 was stopped, the temperature of 
Solution A 1 was elevated to 60.degree. C. spending 60 minutes and 
adjusted to pH 5.0 using a 3% KOH solution. Then, solutions B 1 and C-1 
each were added by means of a double jet method for 42 minutes at a flow 
rate of 55.4 ml/min. The silver potentials (measured by means of a silver 
ion selecting electrode and a saturated silver-silver chloride reference 
electrode) during the temperature elevation from 42.degree. to 60.degree. 
C. and during the re-addition of solutions B-1 and C-1 were regulated to 
+8 mv and 16 mv, respectively, using Solution D 1. 
After the addition, pH was regulated to 6 with 3% KOH. Immediately after 
that, it was subjected to desalting and washing. It was observed by an 
electron microscope that this seed emulsion was composed of hexahedral 
tabular grains, in which 90% or more of the total projected area of silver 
halide grains have a maximum adjacent side ratio of 1.0 to 2.0, having an 
average thickness of 0.064 .mu.m, an average diameter (converted to a 
circle) of 0.595 .mu.m. The deviation coefficient of the thickness is 40%, 
and the deviation coefficient of the distance between the twin planes is 
42%. 
(Preparation of Emulsion Em-1) 
The tabular silver bromide emulsion Em-1 was prepared using the seed 
emulsion 1 and the following four kinds of solutions. 
______________________________________ 
A2 
Ossein gelatin 34.03 g 
Polypropyleneoxy-polyethyleneoxy-disuccinate 
2.25 ml 
sodium salt (10% ethanol solution) 
Seed emulsion 1 amount equivalent to 
1.218 mol 
Water was added to make 3150 ml. 
B2 
Potassium bromide 1747 g 
Water was added to make 3669 ml. 
C2 
Silver nitrate 2493 g 
______________________________________ 
Solution B2 and Solution C2 were added to Solution A2 in 100 minutes at 
60.degree. C. by a double-jet method with vigorous stirring. During this 
process, pH was maintained 5.8, and pAg 8.8. Herein, the addition rate of 
solutions B 2 and C 2 was varied as a function of time to meet a critical 
grain growing rate. That is, the addition was carried out at an 
appropriate addition rate not to produce small grains other than the seed 
grains and not to cause polydispersion due to Ostwald ripening. 
After the addition, the resulting emulsion was cooled to 40.degree. C., 
added with 1800 ml of an aqueous 13.8 weight % solution of modified 
gelatin as a polymer coagulant, which was modified with phenylcarbamoyl 
(substitution rate of 90%), and stirred for 3 minutes. Thereafter, a 56 
weight % acetic acid solution was added to give a pH of 4.6, stirred for 3 
minutes, allowed to stand for 20 minutes, and then the supernant was 
decanted. Thereafter, 9.0 liter of 40.degree. C. distilled water were 
added, stirred, allowed to stand, and the supernant was decanted. To the 
resulting emulsion were added 11.25 liter of distilled water, stirred, 
allowed to stand, and the supernant was decanted. An aqueous gelatin 
solution and a 10 weight % sodium carbonate solution were added to the 
resulting emulsion to be pH of 5.8, and stirred at 50.degree. C. for 30 
minutes to redisperse. 
After the redispersion, the emulsion was adjusted to give pH of 5.80 and 
pAg of 8.06. When the resulting emulsion was observed by means of an 
electron microscope, they were tabular silver halide grains having an 
average diameter of 1.11 .mu.m, an average thickness of 0.25 .mu.m, an 
average aspect ratio of about 4.5 and a grain size distribution of 18.1%. 
The average twin plane distance (a) was 0.020 .mu.m, and variation 
coefficient of (a) was 32%. 
After the resulting emulsion was raised to 60.degree. C., a sensitizing dye 
was added in a given amount in a solid fine particle dispersion, and then 
adenine, ammonium thiocyanate and sensitizers were added. Sixty minutes 
after the addition, the fine grain silver iodide emulsion was added, and 
the emulsion was ripened for total 2 hours. 
After completion of the chemical ripening, 
4-hydroxy-6-methyl-1.3.3a.7-tetrazaindene (TAI) as a stabilizer was added 
in a given amount. 
The addition amount per mol of AgX of the above additives is shown as 
follows. 
______________________________________ 
Spectral sensitizing dye (SD-11) 
2.0 mg 
Spectral sensitizing dye (SD-12) 
120 mg 
Adenine 15 mg 
Ammonium thiocyanide 95 mg 
Sensitizers 
Water-soluble gold compound 
6.5 .times. 10.sup.-6 mol/mol Ag 
(HAuCl.sub.4 .multidot. 4 H.sub.2 O) 
Unstable sulfur compound 
8.1 .times. 10.sup.-6 mol/mol Ag 
(Na.sub.2 S.sub.2 O.sub.3 .multidot. 5 H.sub.2 O) 
Selenium compound (Ph.sub.3 PSe) 
8.1 .times. 10.sup.-6 mol/mol Ag 
Silver iodide fine grain emulsion 
280 mg 
4-Hydroxy-6-methyl-1.3.3a.7-tetrazaindene 
50 mg 
______________________________________ 
SD-11 
##STR21## 
SD-12 
##STR22## 
The solid fine particle dispersions of the spectral sensitizing dyes were 
prepared in a similar manner as a method described in Japanese Patent 
Application No. 4-99437/1996. The dispersion were obtained by adding the 
sensitizing dye in a given amount to 27.degree. C. water and then 
stirring the mixture at 3.500 rpm for 30 to 120 minutes with a high speed 
The silver halide grains contained in the above obtained silver halide 
emulsion (Em-1) had an average silver iodide content of 4 mol % on its 
surface. To the thus sensitized emulsion were added the following 
additives to obtain an emulsion layer coating solution. Further, a 
protective layer coating solution was prepared. 
As a support was used a blue colored 175 .mu.m thick polyethylene 
terephthalate film (a density of 0.15) for X-ray film, both sides of which 
were coated with an aqueous dispersion containing 10 wt % of a copolymer 
of glycidylmethacrylate, methyl acrylate and butyl acrylate (50:10:49, 
weight ratio) to give a subbing layer. 
The following dye layer was coated on both sides of the support, and the 
above emulsion layer coating solution and protective layer coating 
solution were double layer coated in that order on each side of the 
support (a density of 0.15) by means of two slide hopper coaters and 
dried. Thus, silver halide photographic light sensitive material samples 
I-F through I-J, II-F through II-J and III-F through III-J were prepared. 
______________________________________ 
First Layer (Dye Layer) 
Solid dye fine particle dispersion (AH) 
180 mg/m.sup.2 
Gelatin 0.2 g/m.sup.2 
Sodium dodecylbenzene sulfonate 
5 mg/m.sup.2 
Latex (L) 0.2 g/m.sup.2 
Colloidal Silica (average diameter 0.014 .mu.m) 
10 mg/m.sup.2 
Second Layer (Emulsion Layer) 
Emulsion Em-1 obtained above was added with 
the following additives. 
Compound (ST-2) 0.5 mg/m.sup.2 
2,6-Bis(hydroxyamino)-4-diethylamino- 
5 mg/m.sup.2 
1,3,5-triazine 
t-Butyl-catechol 130 g/m.sup.2 
Polyvinyl pyrroridone 35 mg/m.sup.2 
(molecular weight 10,000) 
Styrene-maleic acid anhydride copolymer 
80 mg/m.sup.2 
Poly(sodium styrenesulfonate) 
80 mg/m.sup.2 
Trimethylolpropane 350 mg/m.sup.2 
Diethylene glycol 50 mg/m.sup.2 
Nitrophenyl-triphenyl phosphonium chloride 
20 mg/m.sup.2 
Ammonium 1,3-dihydroxybenzene- 
500 mg/m.sup.2 
4-sulfonic acid 
2-Mercaptobenzimidazole-5-sodiumsulfonate 
5 mg/m.sup.2 
Compound (HS-2) 0.5 mg/m.sup.2 
n-C.sub.4 H.sub.9 OCH.sub.2 CH(OH)CH.sub.2 N(CH.sub.2 COOH).sub.2 
350 mg/m.sup.2 
Compound (ST-3) 5 mg/m.sup.2 
Compound (HS-4) 0.2 mg/m.sup.2 
Compound (ST-5) 5 mg/m.sup.2 
Compound (ST-6) 0.2 mg/m.sup.2 
Collodal Silica 0.5 g/m.sup.2 
(particle size not more than 0.3 .mu.m) 
Latex (L) 0.2 g/m.sup.2 
Dextrin (average molecular weight 1000) 
0.2 g/m.sup.2 
5-methylbenzotriazole 0.7 mg/m.sup.2 
Gelatin 1.0 g/m.sup.2 
Third Layer (Protective Layer) 
Gelatin 0.8 mg/m.sup.2 
4-Hydroxy-6-methyl-1.3.3a.7-tetrazaindene 
20 mg/m.sup.2 
Polymethylmethacrylate matting agent 
50 mg/m.sup.2 
(having an area average grain size of 7.0 .mu.m) 
Latex (L) 0.2 g/m.sup.2 
Polyacrylamide (molecular weight 10,000) 
0.1 g/m.sup.2 
Polysodium acrylate 30 mg/m.sup.2 
Polysiloxane (HS-3) 20 mg/m.sup.2 
Compound (SA-1) 12 mg/m.sup.2 
Compound (SA-2) 2 mg/m.sup.2 
Compound (SA-3) 7 mg/m.sup.2 
Compound (HS-4) 15 mg/m.sup.2 
Compound (SA-4) 15 mg/m.sup.2 
Compound (SA-4) 50 mg/m.sup.2 
Comoound (SA-5) 5 mg/m.sup.2 
C.sub.9 H.sub.19O(CH.sub.2 CH.sub.2 O).sub.11H 
3 mg/m.sup.2 
(C.sub.8 F.sub.17 SO.sub.2)(C.sub.3 H.sub.7)N(CH.sub.2 CH.sub.2 O).sub.15 
H 2 mg/m.sup.2 
(C.sub.8 F.sub.17 SO.sub.2)(C.sub.3 H.sub.7)N(HC.sub.2 CH.sub.2 O).sub.4(C 
H.sub.2).sub.4 SO.sub.3 Na 
1 mg/m.sup.2 
______________________________________ 
Compound ST-2 
##STR23## 
Compound HS-2 
##STR24## 
CompoundSA-1 
##STR25## 
Compound SA-2 
##STR26## 
Compound HS-4 
##STR27## 
Latex (L) 
##STR28## 
Polysiloxane (HS-3) 
##STR29## 
Solid fine particle dispersion dye (F-3) 
##STR30## 
Compound (SA-3) 
##STR31## 
Compound (SA-4) 
C.sub.11 H.sub.23 CONH(CH.sub.2 CH.sub.2 O).sub.5 H 
Compound (SA-5) 
##STR32## 
Compound (ST-3) 
##STR33## 
Compound (ST-4) 
##STR34## 
Compound (ST-5) 
##STR35## 
Compound (ST-6) 
##STR36## 
Antiseptic agent DI-1 was added to each sample above. Inventive 
hardeners and comparative hardener were added to the protective layer 
immediately before coating. The addition amount of the hardeners is an 
amount based on the total gelatin amount (the sum of gelatin added to 
The amount was per one side of the support, and the silver amount was 1.6 
g/m.sup.2 per one side of the support. 
The above obtained samples were fresh samples, and the samples were further 
stored at 50.degree. C. and 50% RH for three days. 
The evaluation was carried out as follows: 
Each sample was sandwiched between two intensifying screens KO-250 
(produced by Konica Corporation), and exposed to X-ray through alminum 
wedge at a tube potential of 80 kvp and at a tube current of 100 mA for 
0.05 seconds. The resulting sample was processed using the following 
developer and fixer in an automatic processor SRX-502 (produced by Konica 
Corporation). 
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Developer composition 
Part A (for 12 liter) 
Potassium hydroxide 450 g 
Potassium sulfite (50% solution) 
2280 g 
Diethylene tetramine pentaacetate 
120 g 
Sodium bicarbonate 132 g 
5-Methylbenzotriazole 1.2 g 
1-Phenyl-5-mercaptotetrazole 
0.2 g 
Hydroquinone 340 g 
Water added to 5000 ml. 
Part B (for 12 liter) 
Glacial acetic acid 170 g 
Triethylene glycol 185 g 
1-Phenyl-3-pyrazolidone 22 g 
5-Nitroindazole 0.4 g 
Starter 
Glacial acetic acid 120 g 
Potassium bromide 225 g 
Water added to 1.0 liter. 
Fixer composition 
Part A (for 18 liter) 
Ammonium thiosulfate (70 wt/vo %) 
6000 g 
Sodium sulfite 110 g 
water acetate.pentahydrate 
450 g 
Sodium citrate 50 g 
Gluconic acid 70 g 
1-(N,N-dimethylamino)ethyl- 
18 g 
5-mercaptotetrazole 
Part B (for 18 liter) 
Aluminum sulfate 800 g 
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Parts A and B were incorporated in 5 liter water while stirring and water 
was added to make 12 liter. The resulting developer was adjusted to pH 
10.40 with glacial acetic acid. Thus, Developer was prepared. 
To 1 liter of the developer were added 20 ml/liter of the starter described 
above and pH was adjusted to 10.40. Thus, developer to be used was 
obtained. 
In preparing fixer, Parts A and B of the fixer composition were 
incorporated in 5 liter water while stirring and water was added to make 
18 liter. The resulting fixer was adjusted to pH 4.4 with surfuric acid 
and NaOH. Thus, fixer replenisher was prepared. 
Regarding processing temperatures, development temperature was 35.degree. 
C., fixing temperature was 33.degree. C., washing temperature was 
20.degree. C., and drying temperature was 50.degree. C. The total 
processing time was 45 seconds in dry to dry time. 
After the processing, sensitivity was measured. Sensitivity was represented 
by a reciprocal of exposure necessary to give a density of fog plus 0.5, 
and sensitivity of samples was represented in terms of sensitivity 
relative to sensitivity of Sample No. I-F stored at 50.degree. C. and 50% 
RH for three days after coating being defined as 100. 
Separate portions of the fresh samples were stored at 50.degree. C. and 50% 
RH for 3 hours, 2 days and 3 days, and each portion was then immersed in 
30.degree. C. water for 5 minutes. A sapphire needle having a radius of 
0.3 mm was brought into pressure contact with the surface of the resulting 
three samples and moved at a rate of 2 mm/second while applying load 
continuously varying from 0 to 200 g. Thus, the load at which the surface 
of the samples was first damaged was designated as surface strength. 
The results are shown in Table 3. 
TABLE 3 
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Photographic 
Hardener properties 
Addition 
Forced aging 
amount 
conditions 
mmol/100 g 
3 days Hardening property 
Sample of (50.degree. C., 50% RH) 
Surface strength (g) 
No. Kinds gelatin 
Sensitivity 
Fog 
3 hrs 
2 days 
3 days 
__________________________________________________________________________ 
I-F I-4 10 100 0.04 
50 56 56 
(INV.) 
I-G I-5 10 100 0.04 
49 55 55 
(INV.) 
I-H I-7 10 101 0.04 
51 57 57 
(INV.) 
I-I I-8 10 98 0.04 
48 54 54 
(INV.) 
I-J I-11 10 100 0.04 
50 56 56 
(INV.) 
II-F II-4 10 100 0.04 
52 58 58 
(INV.) 
II-G II-5 10 99 0.04 
49 55 55 
(INV.) 
II-H II-7 10 100 0.04 
52 57 57 
(INV.) 
II-I II-8 10 99 0.04 
51 56 56 
(INV.) 
II-J II-11 10 99 0.04 
53 58 58 
(INV.) 
III-F 
III-2 10 100 0.04 
50 55 55 
(INV.) 
III-G 
III-3 10 101 0.04 
52 56 56 
(INV.) 
III-H 
III-4 10 99 0.04 
53 58 58 
(INV.) 
III-I 
III-5 10 100 0.04 
51 57 57 
(INV.) 
III-J 
III-7 10 99 0.04 
52 57 57 
(INV.) 
IV-B Comparative 
10 96 0.06 
37 40 46 
(Comp.) 
compound (1) 
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As is apparent from Table 3, Samples I-F through II-J, II-F through II-J 
and III-F through III-J, which employ the hardener of the invention, 
minimize fog increase and sensitivity lowering under the forced aging 
conditions. Accordingly, the hardener of the invention has no adverse 
affect on the photographic properties. 
As is seen from the test results of the hardening property, the surface 
strength of Samples I-F through II-J, II-F through II-J and III-F through 
III-J does not vary after the two day or more storage, but Comparative 
sample IV-B does. Accordingly, the hardener of the invention has no 
after-hardening property.