Silver halide photographic material and color image forming process

A silver halide photographic material is disclosed, which has on a reflective support at least one light-sensitive layer containing silver halide emulsion grains, wherein said reflective support has at least one waterproof resin coated layer which contains at least 2 g/m.sup.2 of a white pigment in waterproof resin coated layer at the light-sensitive layer coated side and further at least one light-sensitive layer contains at least one compound represented by following general formula (I) in a molecular dispersion state of a monomolecule or a dimer; ##STR1## wherein R.sub.1 to R.sub.4 each represent a hydrogen atom or a substituent, the sum total of the atomic weights of at least one of (R.sub.1 +R.sub.3) and (R.sub.2 +R.sub.4) being not more than 160; n represents 0, 1, or 2; and M represents a hydrogen atom or an alkali metal.

FIELD OF THE INVENTION 
The present invention relates to a silver halide photographic material, and 
more particularly to a silver halide photographic material giving no color 
residue by quick processing, being excellent in sharpness, and forming 
less fog by applying a pressure to the light-sensitive photographic 
material before processing. 
BACKGROUND OF THE INVENTION 
Recently, various electronic image-forming means have been developed and 
the image qualities thereof have been compared with those of silver halide 
photographic materials. Also, as the result of the comparison, the high 
image quality and the easiness of the silver halide photographic material 
have been newly recognized. Accordingly, it has been investigated to use 
the silver halide color photographic materials not only for a printing 
material of a photograph but also for a hard copy material of an 
electronic image. In such a circumstance, the investigations of improving 
the sharpness and the color reproducibility to further increase the image 
quality of the silver halide photographic material and improving the 
processing time and the processing process for imparting the easily quick 
processing to the silver halide photographic material have been positively 
made. As to the increase of the easiness and quickening of processing, by 
the progress of an easy quick processing system as shown in a 
mini-laboratory system, print photographs having a very high image quality 
have been supplied relatively easily, in a short time, and at a low cost. 
Furthermore, by using a silver halide emulsion having a high content of 
silver chloride, it has been made to greatly shorten the processing time 
and to improve the processing deviation. 
As a means for improving the sharpness of a silver halide photographic 
material having a reflective support, various means have hitherto been 
known. Examples of the means are 1) the prevention of irradiation by the 
use of a water-soluble dye; 2) the halation prevention by the use of 
colloidal silver, a mordant dye, a solid fine granular dye, etc.; 3) the 
increase of the filling ratio of a white pigment in the laminated resin on 
a paper support, etc. The dye being used for the purposes is, as a matter 
of course, required to not give bad influences on the photographic 
properties such as fog, etc., and is required to quickly be decolored in 
the photographic processing steps. Furthermore, it is preferred that the 
dye is completely decomposed in a processing liquid and does not give bad 
influences such as coloring, etc., to the processing liquid. 
As the dyes meeting the aforesaid condition, the pyrazoloneoxonol dyes 
described, e.g., in British Patent 1,338,799, JP-A-63-264745, 
JP-A-1-196033, JP-A-2-93534, and JP-A-2-97940 have been found. 
However, since the dyes are insufficient in water solubility and the 
molecular weight thereof is increased owing to the dissociative group 
bonded thereto, there is a problem that the diffusing property in the 
photographic layers is low, whereby a sufficient decoloring property is 
not obtained. 
It is disclosed in JP-A-3-156452 (the term "JP-A" as used herein means an 
"unexamined published Japanese patent application") that the sharpness of 
a silver halide photographic material is greatly improved by increasing 
the content of a white pigment in a waterproof resin coated layer at the 
light-sensitive layer coated side of a reflective support. Furthermore, 
JP-A-4-256948, etc., disclose a reflective support having two or more 
polyolefin layers each having a different content of a white pigment. It 
has been found that by the foregoing constitution, the amount of a white 
pigment can be reduced while keeping the sharpness of the silver halide 
photographic material, which is advantageous in cost. 
Also, EP 0,507,489(A1) discloses a reflective support using polyester in 
place of a polyolefin as the waterproof resin forming the coated layer and 
laminated with a mixed composition of the polyester and a white pigment. 
It has been found that in the case of using the laminate of the mixed 
composition of the polyester and a white pigment, the content of a white 
pigment is more increased as compared with the case of using a polyolefin 
as the waterproof resin and that the laminate is very effective for 
improving the sharpness of the silver halide photographic material. 
However, there occurs a new problem that when a pressure such as a scratch, 
etc., is applied to the silver halide photographic material using the 
support wherein the content of a white pigment in the waterproof resin 
coated layer thereof is increased, a fog is liable to form at the pressed 
portions. Also, it has been found that the problem becomes more serious in 
a silver halide emulsion having a very high content of silver chloride. 
SUMMARY OF THE INVENTION 
The object of the present invention is, therefore, to provide a silver 
halide photographic material excellent in developing property and to 
provide a reflective-type photographic light-sensitive material having a 
high content of silver chloride capable of quickly providing a photograph 
having a high image quality at a low cost, said photographic 
light-sensitive material being excellent in sharpness, having a high 
sensitivity, and not causing fog, etc., even when a pressure is applied to 
the photographic light-sensitive material, and also to provide an 
image-forming process capable of quickly forming a photograph having a 
high image quality by using the foregoing reflective-type photographic 
light-sensitive material. 
The object described above can be attained by the following silver halide 
photographic material of the present invention and the following 
image-forming process of the present invention. 
That is, the present invention is as follows. 
(1) A silver halide photographic material having on a reflective support at 
least one light-sensitive layer containing silver halide emulsion grains, 
wherein said reflective support has at least one waterproof resin coated 
layer which contains at least 2 g/m.sup.2 of a white pigment in waterproof 
resin coated layer at the light-sensitive layer coated side and further at 
least one light-sensitive layer contains at least one compound represented 
by following general formula (I) in a molecular dispersion state of a 
monomolecule or a dimer; 
##STR2## 
wherein R.sub.1 to R.sub.4 each represent a hydrogen atom or a 
substituent, the sum total of the atomic weights of at least one of 
(R.sub.1 +R.sub.3) and (R.sub.2 +R.sub.4) being not more than 160; n 
represents 0, 1, or 2; and M represents a hydrogen atom or an alkali 
metal. 
(2) A silver halide photographic material of foregoing (1), wherein the 
substituents R.sub.1, R.sub.2, R.sub.3, and R.sub.4 of the general formula 
(I) do not have a dissociative group. 
(3) A silver halide photographic material of foregoing (2), wherein the 
substituents R.sub.1, R.sub.2, R.sub.3, and R.sub.4 of the general formula 
(I) each are a hydrogen atom or a substituent selected from an alkyl 
group, --COOR.sub.5, --CONR.sub.6 R.sub.7, --CONHR.sub.8, --NR.sub.9 
COR.sub.10, --NR.sub.11 R.sub.12, --CN, --OR.sub.13, and --NR.sub.14 
CONR.sub.15 R.sub.16, wherein R.sub.5 to R.sub.16 each represents a 
hydrogen atom or an alkyl group which may be substituted with a 
substituent having no dissociative group, and R.sub.6 and R.sub.7, 
R.sub.11 and R.sub.12, or R.sub.15 and R.sub.16 may form a ring. 
(4) A silver halide photographic material of foregoing (1), wherein the 
compound shown by the general (I) is a compound represented by following 
general formula (II); 
##STR3## 
wherein R.sub.1, R.sub.6, and R.sub.7 each represent a hydrogen atom or an 
alkyl group which may be substituted, the sum total of the atomic weights 
of R.sub.1, R.sub.6 and R.sub.7 being not more than 120; n represents 0, 
1, or 2; M represents a hydrogen atom or an alkali metal, and R.sub.6 and 
R.sub.7 may combine each other to form a hetero-ring. 
(5) A silver halide photographic material of foregoing (4), wherein the 
substituents R.sub.1, R.sub.6, and R.sub.7 of the general formula (II) do 
not have a dissociative group. 
(6) A silver halide photographic material of foregoing (1) to (5), wherein 
said reflective support is composed of a base material and two or more 
waterproof resin coated layers formed thereon at the light-sensitive 
silver halide emulsion layer coated side, the waterproof resin coated 
layers each have a different content (weight %) of a white pigment. 
(7) A silver halide photographic material of foregoing (6), wherein in the 
two or more waterproof resin coated layers each having a different content 
(weight %) of a white pigment, the content (weight %) of the white pigment 
in the waterproof resin coated layer nearest the base material is lower 
than that of the white pigment in at least one other waterproof resin 
coated layer at the light-sensitive silver halide emulsion layer coated 
side. 
(8) A silver halide photographic material of foregoing (6), wherein in at 
least two waterproof resin coated layers each having a different content 
(weight %) of a white pigment, the content (weight %) of the white pigment 
in the waterproof resin coated layer nearest the light-sensitive layer is 
the highest. 
(9) A silver halide photographic material of foregoing (6), wherein said 
reflective support has at least three waterproof resin coated layers each 
having a different content (weight %) of a white pigment and the content 
(weight %) of the white pigment in the intermediate layer(s) between the 
waterproof resin coated layer nearest the light-sensitive silver halide 
emulsion layer and the waterproof resin coated layer nearest the base 
material is the highest. 
(10) A silver halide photographic material of foregoing (6) to (9), wherein 
the white pigment in the waterproof resin coated layers of the reflective 
support is titanium oxide and a weight ratio of the white pigment to the 
resin in the waterproof resin coated layer having the highest content 
(weight %) of the white pigment is 10/90 to 50/50 (titanium oxide/resin). 
(11) A silver halide photographic material of foregoing (1) to (5), wherein 
the waterproof resin coated layers at the light-sensitive layer coated 
side of said reflective support have a composition prepared by mixing and 
dispersing titanium oxide in a resin composition comprised of a polyester 
synthesized by the condensation polymerization of a dicarboxylic acid and 
a diol, and the weight ratio of titanium oxide to the resin is 10/90 to 
40/60 (titanium oxide/resin). 
(12) A silver halide photographic material of foregoing (11), wherein the 
polyester of said reflective support is a polyester comprised of 
polyethylene terephthalate. 
(13) A silver halide color photographic material of foregoing (1) to (12), 
wherein the light-sensitive silver halide emulsion layers on said 
reflective support are composed of at least three kinds of light-sensitive 
hydrophilic colloid layers each containing one of couplers each coloring 
to yellow, magenta, or cyan and silver halide emulsions which each provide 
a different color sensitivity and each have silver chloride content of at 
least 95 mole%. 
(14) A silver halide photographic material having on a support at least one 
light-sensitive silver halide emulsion layer and at least one 
light-insensitive hydrophilic colloid layer, wherein at least one layer of 
said light-sensitive silver halide emulsion layer and said 
light-insensitive hydrophilic colloid layer contains a compound 
represented by the following general formula (II); 
##STR4## 
wherein R.sub.1, R.sub.6 and R.sub.7 each represent a hydrogen atom or an 
alkyl group which may be substituted, the sum total of the atomic weights 
of R.sub.1, R.sub.6 and R.sub.7 being not more than 120; n represents 0, 1 
or 2; M represents a hydrogen atom or an alkali metal, and R.sub.6 and 
R.sub.7 may combine each other to form a hetero-ring. 
(15) A color image forming process comprising printing the silver halide 
color photographic material described in foregoing (1) through a color 
negative film having a support composed of polyethylene terephthalate or 
polyethylene naphthalate. 
(16) A color image forming process comprising light-exposing the silver 
halide color photographic material described in foregoing (1) by a 
scanning light-exposure system for a light-exposing time shorter than 
10.sup.-4 second per one pixel and thereafter color processing the silver 
halide color photographic material. 
DETAILED DESCRIPTION OF THE INVENTION 
Then, the compound shown by the general formula (I) is explained in detail. 
In the general formula (I) described above, it is necessary that the sum 
total of the atomic weights of at least (R.sub.1 +R.sub.3) and (R.sub.2 
+R.sub.4) is not more than 160 and it is preferred that the sum total of 
the atomic weights of both (R.sub.1 +R.sub.3) and (R.sub.2 +R.sub.4) is 
not more than 160. Also, n is particularly preferred to be 1. 
The substituents R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each are preferably 
selected from a hydrogen atom, an alkyl group, --COOR.sub.5, --CONR.sub.6 
R.sub.7, --CONHR.sub.8, --NR.sub.9 COR.sub.10, --NR.sub.11 R.sub.12, --CN, 
--OR.sub.13, and --NR.sub.14 CONR.sub.15 R.sub.16 (wherein R.sub.5 to 
R.sub.16 each represents a hydrogen atom or an alkyl group which may be 
substituted and said R.sub.6 and R.sub.7, said R.sub.11 and R.sub.12, and 
said R.sub.15 and R.sub.16 may form a ring). 
Furthermore, it is more preferred that the substituents R.sub.1, R.sub.2, 
R.sub.3, and R.sub.4 do not have a dissociative group. 
The "dissociative group" described above is a substituent which is 
substantially dissociated in water of 25.degree. C. and is a dissociative 
group having pKa of not higher than 12. Specific examples of such a 
dissociative group include a sulfonic acid group, a carboxy group, and a 
phosphoric acid group. 
Furthermore, R.sub.1 and R.sub.2 each is preferably a hydrogen atom or an 
alkyl group. The alkyl group is preferably an alkyl group having from 1 to 
3 carbon atoms such as methyl, ethyl, propyl, etc., and the alkyl group 
may have a substituent. As such a substituent, a substituent having an 
unshared electron pair, such as a hydroxy group, an ether group, an ester 
group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a cyano 
group, etc., is preferred and a hydroxy group and an ether group are 
particularly preferred. 
The alkali metal shown by M is preferably Li, Na, K or Cs. 
When R.sub.3 and/or R.sub.4 is an alkyl group, lower alkyl groups such as 
methyl, ethyl, propyl, butyl, etc., are preferred and methyl and ethyl are 
particularly preferred. 
When R.sub.3 and/or R.sub.4 is shown by --COOR.sub.5, the alkyl group shown 
by R.sub.5 is preferably a lower alkyl group such as methyl, ethyl, 
propyl, butyl, etc., and methyl and ethyl are particularly preferred. 
When R.sub.3 and/or R.sub.4 is shown by --CONR.sub.6 R.sub.7, R.sub.6 and 
R.sub.7 may be a hydrogen atom or an alkyl group but it is preferred that 
at least one of R.sub.6 and R.sub.7 is an alkyl group. As the alkyl group, 
methyl, ethyl, propyl, etc., are preferred and the alkyl group may have a 
substituent. As the substituent, a hydroxy group or an ether group is 
preferred. Also, R.sub.6 and R.sub.7 may combine each other to form a ring 
and as the ring formed, a morpholine ring is particularly preferred. 
When R.sub.3 and/or R.sub.4 is shown by --CONHR.sub.8 and R.sub.8 is an 
alkyl group, the alkyl group has the same meaning as the alkyl group shown 
by R.sub.6 and R.sub.7. 
When R.sub.3 and/or R.sub.4 is shown by --NR.sub.9 COR.sub.10, R.sub.9 and 
R.sub.10 may be a hydrogen atom or an alkyl group. As the alkyl group, 
methyl, ethyl, propyl, etc., are preferred and methyl is particularly 
preferred. The alkyl group may have a substituent and as the substituent, 
a hydroxy group and an ether group are preferred. 
When R.sub.3 and/or R.sub.4 is shown by --NR.sub.11 R.sub.12 or 
--OR.sub.13, R.sub.11, R.sub.12, and R.sub.13 may be a hydrogen atom or an 
alkyl group. As the alkyl group, methyl, ethyl, propyl, etc., are 
preferred and the alkyl group may have a substituent. As the substituent, 
a hydroxy group and an ether group are preferred. Also, R.sub.11 and 
R.sub.12 may combine each other to form a ring. 
When R.sub.3 and/or R.sub.4 is shown by --NR.sub.14 CONR.sub.15 R.sub.16, 
R.sub.14, R.sub.15, and R.sub.16 may be a hydrogen atom or an alkyl group. 
As the alkyl group, methyl, ethyl, propyl, etc., are preferred and methyl 
is particularly preferred. Also, the alkyl group may have a substituent. 
As the substituent, a hydroxy group and an ether group are preferred. 
In the substituents R.sub.3 and R.sub.4, --CONR.sub.6 R.sub.7 is 
particularly preferred. R.sub.6 and R.sub.7 preferably combine each other 
to form a 5- or 6-membered ring. As the ring thus formed, there are a 
morpholine ring, a piperidine ring, a pyrrolidine ring, and a pyridazine 
ring but a morpholine ring is particularly preferred. The alkyl group 
represented by R.sub.1 in the general formula (II) preferably includes 
methyl group and ethyl group, which may be substituted by a substituent 
such as cyano group and hydroxy group, but is particularly preferred to 
have no substituent. 
It is preferred that the dye in the present invention exists in a molecular 
dispersion state of a monomolecule or a dimer. The molecular dispersion 
state is the state that the compound shown by the general formula (I) 
described above is uniformly dispersed in a silver halide emulsion layer 
or other hydrophilic colloid layer and when the dispersion state is 
observed by an electron microscope at a 100,000 magnification, 
substantially no solid is detected. 
Then, specific examples of the compound shown by the general formula (I) 
being used in the present invention are illustrated below but the compound 
is not limited thereto. 
______________________________________ 
##STR5## 
R.sup.1 R.sup.2 n M 
______________________________________ 
1 H CONHCH.sub.2 CH.sub.2 OH 
0 K 
2 H CON(CH.sub.3).sub.2 
1 K 
3 H 
##STR6## 1 K 
4 CH.sub.3 CONHCH.sub.2 CH.sub.2 OCH.sub.3 
1 K 
5 CH.sub.2 CH.sub.3 
CONHCH.sub.2 CH.sub.2 OH 
1 K 
6 CH.sub.2 CH.sub.2 OH 
##STR7## 1 K 
7 CH.sub.2 CH.sub.2 OH 
CONHCH.sub.2 CH.sub.2 OH 
0 K 
8 CH.sub.2 CH.sub.2 OH 
CONHCH.sub.3 1 K 
9 H CONHCH.sub.2 CH.sub.2 OH 
1 K 
10 H CON(CH.sub.3).sub.2 
2 K 
11 CH.sub.3 
##STR8## 1 Na 
12 CH.sub.3 CONHCH.sub.2 CH.sub.2 OCH.sub.3 
2 K 
13 CH.sub.2 CH.sub.3 
CONHCH.sub.2 CH.sub.2 OH 
2 K 
14 CH.sub.2 CH.sub.2 OH 
##STR9## 2 K 
15 CH.sub.2 CH.sub.2 OH 
CONHCH.sub.2 CH.sub.2 OH 
2 K 
16 CH.sub.2 CH.sub.2 OH 
CONHCH.sub.3 2 K 
17 H COOC.sub.2 H.sub.5 
0 K 
18 H COOCH.sub.3 1 K 
19 CH.sub.3 COOC.sub.2 H.sub.5 
1 Na 
20 CH.sub.3 COOCH.sub.2 CH.sub.2 OCH.sub.3 
1 K 
21 CH.sub.2 CH.sub.3 
COOC.sub.2 H.sub.5 
0 K 
22 CH.sub.2 COOC.sub.2 H.sub.5 
COOC.sub.2 H.sub.5 
1 K 
23 CH.sub.2 CH.sub.2 OH 
COOC.sub.2 H.sub.5 
1 K 
24 H COOC.sub.2 H.sub.5 
1 K 
25 H COOCH.sub.3 2 K 
26 CH.sub.3 COOC.sub.2 H.sub.5 
2 K 
27 CH.sub.3 COOCH.sub.2 CH.sub.2 OCH.sub.3 
2 K 
28 CH.sub.2 CH.sub.3 
COOC.sub.2 H.sub.5 
2 K 
29 CH.sub.2 COOC.sub.2 H.sub.5 
COOC.sub.2 H.sub.5 
2 K 
30 CH.sub.2 CH.sub.2 OH 
COOC.sub.2 H.sub.5 
2 K 
31 H CN 0 K 
32 H CN 1 K 
33 CH.sub.3 CN 0 K 
34 CH.sub.3 CN 1 K 
35 CH.sub.2 CH.sub.3 
CN 1 K 
36 CH.sub.2 CH.sub.3 
CN 2 K 
37 H CN 2 K 
38 CH.sub.3 CN 2 K 
39 H CH.sub.3 1 K 
40 H CH.sub.2 CH.sub.3 
1 K 
41 CH.sub.3 H 1 Na 
42 CH.sub.3 CH.sub.3 0 K 
43 CH.sub.2 CH.sub.2 
CH.sub.3 1 K 
44 CH.sub.2 COOC.sub.2 H.sub.5 
CH.sub.3 1 K 
45 CH.sub.2 CH.sub.2 OH 
CH.sub.3 1 K 
46 CH.sub.2 CH.sub.2 OH 
CH.sub.2 CH.sub.3 
1 K 
47 H CH.sub.3 2 K 
48 H CH.sub.2 CH.sub.3 
2 K 
49 CH.sub.3 H 2 K 
50 CH.sub.3 CH.sub.3 2 K 
51 CH.sub.2 CH.sub.3 
CH.sub.3 2 K 
52 CH.sub.2 COOC.sub.2 H.sub.5 
CH.sub.3 2 K 
53 CH.sub.2 CH.sub.2 OH 
CH.sub.3 2 K 
54 CH.sub.2 CH.sub.2 OH 
CH.sub.2 CH.sub.3 
2 K 
55 H OC.sub.2 H.sub.5 
1 K 
56 H OC.sub.2 H.sub.5 
2 K 
57 CH.sub.3 OC.sub.2 H.sub.5 
2 K 
58 CH.sub.3 OH 1 K 
59 CH.sub.2 CH.sub.3 
OC.sub.2 H.sub.5 
2 K 
60 CH.sub.2 COOC.sub.2 H.sub.5 
OC.sub.2 H.sub.5 
2 K 
61 CH.sub.2 CH.sub.2 OH 
OC.sub.2 H.sub.5 
1 K 
62 CH.sub.2 CH.sub.2 OH 
OC.sub.2 H.sub.5 
2 K 
63 H OC.sub.2 H.sub.5 
0 K 
64 H OCH.sub.2 CH.sub.2 OH 
1 K 
65 CH.sub.3 OC.sub.2 H.sub.5 
0 K 
66 CH.sub.3 OH 2 K 
67 CH.sub.2 CH.sub.3 
OC.sub.2 H.sub.5 
1 K 
68 CH.sub.2 COOC.sub.2 H.sub.5 
OC.sub.2 H.sub.5 
1 K 
69 CH.sub.2 CH.sub.2 OH 
OC.sub.2 H.sub.5 
0 K 
70 CH.sub.2 CH.sub.2 OH 
OCH.sub.2 CH.sub.2 OH 
1 K 
71 H NH.sub.2 0 K 
72 H NHCH.sub.2 CH.sub.2 OH 
1 K 
73 CH.sub.3 NHCH.sub.2 CH.sub.2 OH 
0 K 
74 CH.sub.3 NHCH.sub.2 CH.sub.2 OH 
1 K 
75 CH.sub.2 CH.sub.3 
NHCH.sub.2 CH.sub.2 OH 
1 K 
76 CH.sub.2 COOC.sub.2 H.sub.5 
NHCH.sub.2 CH.sub.2 OH 
1 K 
77 CH.sub.2 CH.sub.2 OH 
NHCH.sub.2 CH.sub.2 OH 
0 K 
78 CH.sub.2 CH.sub.2 OH 
NHCH.sub.2 CH.sub.2 OH 
1 K 
79 H NH.sub.2 1 K 
80 H NHCH.sub.2 CH.sub.2 OH 
2 K 
81 CH.sub.3 NHCH.sub.2 CH.sub.2 OH 
2 K 
82 CH.sub.3 NH.sub.2 1 K 
83 CH.sub.2 CH.sub.3 
NHCH.sub.2 CH.sub.2 OH 
2 K 
84 CH.sub.2 COOC.sub.2 H.sub.5 
NHCH.sub.2 CH.sub.2 OH 
2 K 
85 CH.sub.2 CH.sub.2 OH 
NHCH.sub.2 CH.sub.2 OH 
2 K 
86 CH.sub.2 CH.sub.2 OH 
NH.sub.2 1 K 
87 H NHCOCH.sub.3 1 K 
88 H NHCOCH.sub.3 2 K 
89 CH.sub.3 NHCOCH.sub.3 1 Na 
90 CH.sub.3 NHCOCH.sub.3 2 K 
91 CH.sub.2 CH.sub.3 
NHCOCH.sub.3 1 K 
92 CH.sub.2 COOCH.sub.3 
NHCOCH.sub.3 1 K 
93 CH.sub.2 CH.sub.2 OH 
NHCOCH.sub.3 1 K 
94 CH.sub.2 CH.sub.2 OH 
NHCOCH.sub.3 2 K 
95 H NHCONHCH.sub.3 0 K 
96 H NHCONHCH.sub.3 1 K 
97 CH.sub.3 NHCONHCH.sub.3 0 K 
98 CH.sub.3 NHCONHCH.sub.3 1 K 
99 CH.sub.2 CH.sub.3 
NHCONHCH.sub.3 1 K 
100 H NHCONHCH.sub.3 2 K 
101 H NHCON(CH.sub.3).sub.2 
1 K 
102 CH.sub.3 NHCONHCH.sub.3 2 K 
103 CH.sub.3 NHCON(CH.sub.3).sub.2 
2 K 
104 CH.sub.2 CH.sub.3 
NHCONHCH.sub.3 2 K 
______________________________________ 
(105) 
##STR10## 
(106) 
##STR11## 
(107) 
##STR12## 
(108) 
##STR13## 
(109) 
##STR14## 
(110) 
##STR15## 
(111) 
##STR16## 
(112) 
##STR17## 
(113) 
##STR18## 
(114) 
##STR19## 
(115) 
##STR20## 
(116) 
##STR21## 
(117) 
##STR22## 
(118) 
##STR23## 
______________________________________ 
The compound shown by the general formula (I) being used in the present 
invention can be molecular dispersed in a light-sensitive layer or 
light-insensitive layer by various known methods. That is, there are a 
method of directly dispersing the compound in a light-sensitive layer or a 
light-insensitive layer, a method of dissolving the compound in a proper 
solvent (e.g., methanol, ethanol, propanol, methyl cellosolve, the 
halogenated alcohols described in JP-A-48-9715 and U.S. Pat. No. 
3,756,830, acetone, water, pyridine, mixture thereof) and adding the 
compound in a form of the solution thereof, etc. 
When the compound of the general formula (I) being used in the present 
invention is added to any of the light-sensitive layers and 
light-insensitive layers, the compound diffuses so as to be uniformly 
dispersed in the whole layers constituting the photographic 
light-sensitive material of the present invention. 
There is no particular restriction in an amount of the compound represented 
by formula (I) being used in the present invention but is used in the 
range of preferably from 0.1 mg/m.sup.2 to 200 mg/m.sup.2, and 
particularly preferably from 1 mg/m.sup.2 to 100 mg/m.sup.2. 
The compound shown by the general formula (II) can be synthesized by the 
reaction of the compound of the general formula (A) and a methine source 
as shown in following reaction formula 1. 
##STR24## 
The compound shown by the general formula (A) is obtained by reacting an 
3-alkoxycarbonyl-5-hydroxypyrazole synthesized from oxalacetic ester and 
hydrazine with a nitrogen-containing compound such as morpholine as shown 
in following reaction formula 2. 
##STR25## 
Specific examples of the pyrazole compound of the present invention are 
shown below. 
##STR26## 
Then, the reflective support being used in the present invention is 
explained in detail. 
It is necessary that the reflective support being used in the present 
invention contains at least 2 g/m.sup.2 of a white pigment in total in the 
waterproof resin coated layer or layers at the light-sensitive layer 
coated side of the reflective support. If the content of the white pigment 
is less than 2 g/m.sup.2, the sharpness of the photographic 
light-sensitive material is greatly reduced and the object of the present 
invention can not be attained. The content of the white pigment is 
preferably at least 3.0 g/m.sup.2, and more preferably at least 4.0 
g/m.sup.2. There is no particular restriction on the upper limit of the 
white pigment but the content of the white pigment is preferably not more 
than 30 g/m.sub.2 from the view point of cost. 
As the white pigment being mixed and dispersed in the waterproof resin, 
there are inorganic pigments such as titanium dioxide, barium sulfate, 
lithophone, aluminum oxide, calcium carbonate, silicon oxide, antimony 
trioxide, titanium phosphate, zinc oxide, white lead, zirconium oxide, 
etc., and fine powders of an organic material such as polystyrene, a 
styrene-divinylbenzene copolymer, etc. 
In these pigments, the use of titanium dioxide is particularly effective. 
Titanium dioxide may be of a rutile type or an anatase type but in the 
case of preceding the whitens, anatase-type titanium dioxide is preferably 
used and in the case of preceding the sharpness, rutile-type titanium 
dioxide is preferably used. For improving both the whiteness and the 
sharpness, a blend of anatase-type titanium dioxide and rutile-type 
titanium dioxide may be used. Furthermore, when the waterproof resin 
coated layer is composed of plural layers, a method of using anatase-type 
titanium dioxide for a certain layer and rutile-type titanium dioxide for 
other layer can be preferably employed. Also, titanium dioxide may be one 
produced by a sulfate method or a chloride method. Moreover, titanium 
dioxide being used in the present invention is also commercially available 
as KA-10, KA-20, etc., trade names, made by Titanium Kogyo K.K., and 
A-220, etc., trade name, made by Ishihara Sangyo Kaisha, Ltd. 
Titanium dioxide being used in the present invention is preferably 
surface-treated with an inorganic material such as aluminum hydroxide, 
silicon hydroxide, etc.; an organic material such as a polyhydric alcohol, 
a polyvalent amine, a metal soap, an alkyl titanate, polysiloxane, etc.; 
or a combination of the inorganic material and the organic material, in 
order to restrain the activation of titanium dioxide to prevent the 
occurrence of yellowing. The amount of the surface-treating material is 
preferably from 0.2% by weight to 2.0% by weight to titanium dioxide for 
the inorganic material and from 0.1% by weight to 1.0% by weight to 
titanium dioxide for the organic material. 
The mean particle size of titanium dioxide being used in this invention is 
preferably from 0.1 .mu.m to 0.8 .mu.m. If the mean particle size of 
titanium dioxide is less than 0.1 .mu.m, it becomes undesirably difficult 
to uniformly mix and disperse it in the resin, while if the mean particle 
size if over 0.8 .mu.m, a sufficient whiteness is not obtained and also 
projections are formed on the coated surface to give bad influences on the 
image quality formed. 
In the present invention, it is preferred that the fine particles of the 
white pigment do not form aggregates, etc., of the particles in the 
reflective layer and are uniformly dispersed therein and the extent of the 
particle distribution can be obtained by measuring areal population (%) 
(Ri) of the fine particles projected onto a unit area. The coefficient of 
variation of the areal population (%) can be obtained by the ratio s/R of 
the standard deviation s of Ri to the average value (R) of Ri. In the 
present invention, the variation coefficient of the areal population (%) 
of the fine particles of the white pigment is preferably not higher than 
0.15, more preferably not higher than 0.12, and particularly preferably 
not higher than 0.08. 
The waterproof resin for the reflective support being used in the present 
invention is a resin having a water absorption (weight %) of not higher 
than 0.5, and preferably not higher than 0.1. Examples of the waterproof 
resin are polyolefins such as polyethylene, polypropylene, a polyethylene 
series polymer, etc.; a vinyl polymer and the copolymers thereof (e.g., 
polystyrene, polyacrylate, and the copolymers thereof), polyesters 
(polyethylene terephthalate, polyethylene isophthalate, etc.) and the 
copolymers thereof. In these resins, polyethylene and polyesters are 
particularly preferred. 
As polyethylene, high-density polyethylene, low-density polyethylene, 
linear low-density polyethylene, and blend of these polyethylenes can be 
used. The melt flow rate (hereinafter, is referred to as MFR) of the 
polyethylene resin described above before working is in the range of 
preferably from 1.2 g/10 minutes to 12 g/10 minutes as the value measured 
under Condition 4 of Table 1 of JISK 7210. MFR of the polyolefin resin 
before working in the present invention is MFR of the resin before 
kneading therewith a bluing agent and the white pigment. 
As the polyester, a polyester synthesized by the condensation 
polymerization of a dicarboxylic acid and a diol is preferred. As the 
dicarboxylic acid, there are terephthalic acid, isophthalic acid, 
naphthalenedicarboxylic acid, etc. Also, as the preferred diol, there are 
ethylene glycol, butylene glycol, neopentyl glycol, triethylene glycol, 
butanediol, hexylene glycol, a bisphenol A-ethylene oxide addition product 
[2,2-bis(4-(2-hydroxyethyloxy)phenyl)propane], 
1,4-dihydroxymethylcyclohexane, etc. 
Various polyesters obtained by condensation polymerization of the 
dicarboxylic acid singly or a mixture of these dicarboxylic acid and the 
diol singly or a mixture of these diols can be used in the present 
invention. In these polyesters, it is preferred that at least one kind of 
the dicarboxylic acids is terephthalic acid. Also, as the dicarboxylic 
acid component, a mixture of terephthalic acid and naphthalenedicarboxylic 
acid (mole ratio of from 9:1 to 2:8) or a mixture of terephthalic acid and 
naphthalenedicarboxylic acid (mole ratio of from 9:1 to 2:8) is preferably 
used. 
Also, as the diol component, ethylene glycol or a mixed diols containing 
ethylene glycol is preferably used. The molecular weights of these 
polymers are preferably from 30,000 to 50,000. 
Also, a mixture of these plural kinds of polyesters each having a different 
composition is preferably used. Furthermore, a mixture of the polyester(s) 
and other resin(s) can be preferably used. As the resin which can be used 
as the mixture with the polyester(s), resin which can be extruded at a 
temperature of from 270.degree. C. to 350.degree. C., for example, 
polyolefins such as polyethylene, polypropylene, etc.; polyethers such as 
polyethylene glycol, polyoxymethylene, polyoxypropylene, etc.; polyester 
series polyurethane; polyester series polyurethane; polycarbonate; and 
polystyrene can be widely used. 
These resins being blended may be one kind of resin or two or more kinds of 
resins. For example, 6% by weight polyethylene and 4% by weight 
polypropylene can be mixed with 90% by weight polyethylene terephthalate. 
The mixing ratio of the polyester and other resin(s) depends upon the kind 
of the other resin(s) to be mixed but when the other resin is a 
polyolefin, the mixing ratio of polyester/other resin is suitably from 
100:0 to 80:20 by weight ratio. If the mixing ratio is over the range, the 
properties of the mixed resins are rapidly reduced. When the resin to be 
blended with the polyester is a resin other than the polyolefin, the 
mixing ratio of polyester/other resin is in the range of from 100:0 to 
50:50 by weight ratio. 
The ratio of the foregoing waterproof resin to the white pigment which is 
used in the whole waterproof resin layers of the photographic material of 
the present invention is from 98/2 to 30/70, preferably from 95/5 to 
50/50, and particularly preferably from 90/10 to 60/40 (waterproof 
resin/white pigment) by weight ratio. If the mixing ratio of the white 
pigment is less than 2% by weight, the contribution to the whiteness is 
insufficient, if the mixing ratio is over 70% by weight, the surface 
smoothness as the support for the photographic light-sensitive material is 
insufficient, thereby a support for the photographic light-sensitive 
material excellent in surface gloss can not be obtained. 
The waterproof resin layer(s) are coated on a base material at the 
light-sensitive layer coated side in a total thickness of preferably from 
2 .mu.m to 200 .mu.m, and more preferably from 5 .mu.m to 80 .mu.m. If the 
thickness thereof is thicker than 200 .mu.m, there occurs a problem in 
physical properties such that the resin becomes very brittle to cause 
cracks, etc. If the thickness thereof is thinner than 2 .mu.m, the water 
proofing property, which is the fundamental object of the coating, is 
spoiled as well as it becomes impossible to simultaneously satisfy the 
whiteness and the surface smoothness of the support and also the resin 
layer becomes undesirably too soft in physical property. 
In the silver halide photographic material of the present invention, the 
reflective support also has a resin layer at the back side (opposite side 
to the light-sensitive layer coated side) and the thickness of the resin 
or a resin composition being coated at the back side is preferably from 5 
.mu.m to 100 .mu.m, and more preferably from 10 .mu.m to 50 .mu.m. If the 
thickness thereof is over the range, there occurs a problem in physical 
properties such that the resin becomes very brittle to cause cracks, etc. 
If the thickness is thinner than the range, the water proofing property, 
which is the fundamental object of the coating is spoiled and also the 
resin layer becomes undesirably too soft in physical property. 
In the reflective support being used in the present invention, it is, as 
the case may be, preferable from the view points of cost, the production 
aptitude of the support, etc., that the waterproof resin coated layer at 
the light-sensitive layer coated side of the support is composed of two or 
more waterproof resin coated layers each having a different content of the 
white pigment. In this case, it is preferred that in the waterproof resin 
coated layers each having a different content of the white pigment, the 
content of the white pigment in the waterproof resin coated layer nearest 
the base material is lower than the content of the white pigment than at 
least one other waterproof resin coated layer disposed above the foregoing 
layer. As a more preferred embodiment, there is a reflective support 
wherein in the waterproof resin coated layers each having a different 
content of the white pigment, the content of the white pigment in the 
waterproof resin coated layer nearest the light-sensitive silver halide 
emulsion layer is the highest or a reflective support wherein the 
waterproof resin coated layers each having a different content of the 
white pigment are composed of at least three waterproof resin coated 
layers and the content of the white pigment in the intermediate layer or 
one of the intermediate layers between the waterproof resin coated layer 
nearest the light-sensitive silver halide emulsion layer and the 
waterproof resin coated layer nearest the base material. 
In the multilayer waterproof resin coated layers, the content of the white 
pigment in each layer is from 0% by weight to 70% by weight, preferably 0% 
by weight to 50% by weight, and more preferably from 0% by weight to 40% 
by weight. The content of the white pigment in the layer having the 
highest content of white pigment of the multilayer waterproof resin coated 
layers is from 10% by weight to 70% by weight, preferably from 10% by 
weight to 50% by weight, more preferably from 15% by weight to 50% by 
weight and most preferably from 20% by weight to 40% by weight. If the 
content of the white pigment in the layer having the highest content of 
the white pigment is less than 9% by weight, the sharpness of the image 
formed is low, while if the content thereof is over 70% by weight, the 
film of the resin formed by melt extrusion causes cracks. 
Also, the thickness of each layer of the multilayer waterproof resin coated 
layers is preferably from 0.5 .mu.m to 50 .mu.m. For example, in the case 
of the multilayer waterproof resin coated layers of a two-layer 
construction, the thickness of each layer is preferably from 0.5 .mu.m to 
50 .mu.m and the total thickness of the layers is preferably in the 
foregoing range (i.e., 2 .mu.m to 200 .mu.m). 
In the case of the multilayer waterproof resin coated layer of a 
three-layer construction, it is preferred that the thickness of the 
uppermost layer is from 0.5 .mu.m to 10 .mu.m, the thickness of the 
interlayer is from 5 .mu.m to 50 .mu.m, and the thickness of the lowermost 
layer (the layer nearest the base material) is from 0.5 .mu.m to 10 .mu.m. 
If the thickness of each of the uppermost layer and the lowermost layer is 
thinner than 0.5 .mu.m, die lip stripes are liable to cause by the action 
of the white pigment highly filled in the interlayer. 
On the other hand, if the thickness of each of the uppermost layer and the 
lowermost layer, in particular, the thickness of the uppermost layer is 
thicker than 10 .mu.m, the sharpness of the photographic light-sensitive 
material is liable to lower. 
The waterproof resin is mixed with the white pigment by kneading the white 
pigment in the resin by a kneading machine such as double rolls, 
three-rolls, a kneader, a bambury mixer, etc., using a metal salt of a 
higher fatty acid, a higher fatty acid ethyl ester, a higher fatty acid 
amide, a higher fatty acid, etc., as a dispersion aid. The amount of the 
dispersion aid is generally from about 0.5% by weight to 10% by weight to 
the white pigment. The resin layer(s) can contain an antioxidant and the 
proper content of the antioxidant is from 50 ppm to 100 ppm to the resin. 
Also, it is preferred that the waterproof resin coated layer(s) contain a 
blueing agent. As the blueing agent, generally known materials such as 
ultramarine blue, cobalt blue, cobalt oxyphosphate, quinacridone series 
pigments, etc., and mixtures thereof are used. 
There is no particular limitation on the particle sizes of the blueing 
agent but the particle sizes of commercially available blueing agents are 
usually from about 0.3 .mu.m to 10 .mu.m and the blueing agent having the 
particle sizes of the range can be used without any hindrance. 
When the waterproof resin coated layer of the reflective support being used 
in the present invention is a multilayer structure, it is preferred that 
the content of the blueing agent in the uppermost waterproof resin coated 
layer is higher than the content of the blueing agent in the lower 
layer(s). In this case, it is preferred that the content of the blueing 
agent in the uppermost waterproof resin coated layer is from 0.2% by 
weight to 0.5% by weight and the content thereof in the lower layer is 
from 0 to 0.45% by weight. 
The blueing agent is kneaded in the waterproof resin by a kneading machine 
such as double rollers, three-rollers, a kneader, a bambury mixer, etc. In 
this case, the blueing agent can be kneaded in the waterproof resin 
together with the white pigment. Also, for improving the dispersibility of 
the blueing agent, a dispersion aid such as a waterproof resin having a 
low molecular weight, a metal salt of a higher fatty acid, a higher fatty 
acid ester, a higher fatty acid amide, a higher fatty acid, etc., can be 
used. 
As the method of forming the waterproof resin coated layers in the present 
invention, pellets containing the foregoing white pigment and/or the 
blueing agent are melted and, after, if necessary, diluting the molten 
pellets with a heat resisting resin followed by melting, are formed on a 
continuously travelling base material, e.g., a base paper such as a paper, 
a synthetic paper, etc., and a plastic film such as a polyester film 
(e.g., a polyethylene terephthalate film and a polybutylene terephthalate 
film), a polyolefin film (e.g., a polyester film, a triacetyl cellulose 
film, and a polypropylene film), etc., by a successive laminating method 
or a laminating method using a multilayer extruding die of a feed block 
type, a multimanifold type, or a multislot type. As the form of the die 
for multilayer extruding. a T die, a coat hanger die, etc., is general and 
there is no particular restriction on the form. 
The outlet temperature at melt extrusion of the waterproof resin is usually 
from 270.degree. C. to 350.degree. C., and preferably from 300.degree. C. 
to 330.degree. C. Also, it is preferred to apply an activation treatment 
such as a corona discharging treatment, a flame treatment, a glow 
discharging treatment, etc., to the base material before coating the resin 
on the base material. 
On the surface of the uppermost layer of the waterproof resin coated layers 
at the silver halide emulsion coating side of the reflective support can 
be applied marking of a gloss surface or marking of a fine surface, a 
matted surface or a silk surface described in JP-A-55-26507 and also on 
the back surface can be applied marking of a matt surface. 
Also, it is preferred to apply an activation treatment such as a corona 
discharging treatment, a flame treatment, a plasma treatment, etc., onto 
the surface of the waterproof resin coated layer and further after the 
activation treatment, it is preferred to apply thereon a subbing treatment 
as described in JP-A-61-84643. 
It is also preferred to coat a subbing liquid containing a compound 
represented by following general formula [U]. 
##STR27## 
wherein n is an integer of from 1 to 7. 
The coating amount of the compound shown by the general formula [U] is 
preferably at least 0.1 mg/m.sup.2, more preferably at least 1 mg/m.sup.2, 
and most preferably at least 3 mg/m.sup.2. If the coating amount of the 
compound is larger, the adhesive force can be more increased but the use 
of an excessive amount of the compound is disadvantageous in cost. 
Also, for improving the coating aptitude of the subbing liquid, it is 
preferred to add an alcohol such as methanol, etc., to the subbing liquid. 
In this case, the content of the alcohol is preferably at least 20% by 
weight, more preferably at least 40% by weight, and most preferably at 
least 60% by weight. 
Also, for further improving the coating aptitude of the subbing liquid, it 
is preferred to add thereto various kinds of surface active agents such as 
an anionic surface active agent, a cationic surface active agent, an 
amphoteric surface active agent, a nonionic surface active agent, a 
fluorocarbon series surface active agent, an organosilicon series surface 
active agent, etc. 
Also, for obtaining a good subbing coated surface form, it is preferred to 
add a water-soluble high molecular material such as gelatin, etc., to the 
subbing liquid. 
For the stability of the compound shown by the general formula [U], pH of 
the subbing liquid is preferably from 4 to 11, and more preferably from 5 
to 10. 
It is more preferred to apply the surface activation treatment as described 
above to the surface of the waterproof resin coated layer before coating 
thereon the foregoing subbing liquid. 
The subbing liquid can be coated by a generally well-known coating method 
such as gravure coating method, a bar coater coating method, a dip coating 
method, an air knife coating method, a curtain coating method, roller 
coating method, a doctor coating method, an extrusion coating method. 
The drying temperature of the coating is preferably from 30.degree. C. to 
100.degree. C., more preferably from 50.degree. C. to 100.degree. C., and 
most preferably from 70.degree. C. to 100.degree. C. The upper limit of 
the drying temperature is determined by the heat resistance of the resin 
and the lower limit thereof is determined by the efficiency of 
productivity. 
As the base material being used for the reflective support in the present 
invention, a natural pulp paper composed of a natural pulp as the main raw 
material, a paper made from a mixture of a natural pulp and synthetic 
fibers, a synthetic fiber paper composed of synthetic fibers as the main 
component, a so-called synthetic paper, that is, a peudopaper-like 
synthetic resin film of polystyrene, polypropylene, etc., a plastic film 
such as a polyester film (e.g., a polyethylene terephthalate film and a 
polybutylene terephthalate film), a polyolefin film (e.g., a triacetyl 
cellulose film, a polystyrene film, and polypropylene film), etc., are 
used. Of them, as the base material for photographic waterproof resin 
coating, a natural pulp paper (hereinafter, is referred to simply as a 
base paper) is particularly advantageously used. 
Various additives can be added to the base paper and as such additives, 
there are fillers such as clay, talc, calcium carbonate, fine particles of 
a urea resin, etc.; sizes such as rosin, an alkylketene dimer, a higher 
fatty acid, an epoxidated fatty acid amide, paraffin wax, an 
alkenylsuccinic acid, etc.; paper strength reinforcing agents such as 
starch, polyamidopolyamine epichlorohydrin, polyacrylamide, etc.; fixing 
agents such as aluminum sulfate, a cationic polymer, etc. If necessary, 
other additives such as dyes, fluorescent dyes, slime controlling agents, 
defoaming agents, etc., are added thereto. Also, if necessary, the 
following softeners can be added to the base paper. 
The softeners are described, e.g., in Shin Kami Kako Binran (New Paper 
Working Handbook), pages 554 to 555 (published by Shiyaku Times K.K., 
1980). In particular, the softeners having a molecular weight of at least 
200 are preferred. That is, the softener has a hydrophobic group having at 
least 10 carbon atoms and an amine salt or a quaternary ammonium salt 
self-fixing with cellulose. Practically, there are a reaction product of a 
maleic anhydride copolymer and a polyalkylenepolyamine, a reaction product 
of a higher fatty acid and a polyalkylenepolyamine, a reaction product of 
urethane alcohol and an alkylating agent, a quaternary ammonium salt of a 
higher fatty acid, etc., but the reaction product of a maleic anhydride 
copolymer and a polyalkylenepolyamine and the reaction product of urethane 
alcohol and an alkylating agent are particularly preferred. 
Onto the surface pulp can be applied a surface sizing treatment with a 
film-forming polymer such as gelatin, starch, carboxymethyl cellulose, 
polyacrylamide, polyvinyl alcohol, a denatured product of polyvinyl 
alcohol, etc. 
As the denatured product of polyvinyl alcohol described above, there are a 
carboxy group-denatured product, a silanol-denatured product, a copolymer 
with acrylamide, etc. 
Also, in the case of surface sizing treatment with a film-forming polymer, 
the coating amount of the film-forming polymer is from 0.1 g/m.sup.2 to 
5.0 g/m.sup.2, and preferably from 0.5 g/m.sup.2 to 2.0 g/m.sup.2. 
Furthermore, in this case, the film-forming polymer may contain, if 
necessary, an antistatic agent, a fluorescent brightening agent, a 
pigment, a defoaming agent, etc. 
The base paper is produced by making paper using a pulp slurry containing 
the foregoing pulp together with, if necessary, a filler, a size, a paper 
strength reinforcing agent, a fixing agent, etc., by a paper machine such 
as a Fourdrinier paper machine, drying, and winding. In this case, it is 
preferred that before or after drying the paper, the foregoing surface 
sizing treatment is applied and also between after drying and winding, 
calendering treatment is applied. When the surface sizing treatment is 
applied after drying, the calendaring treatment can be practiced before or 
after the surface sizing treatment but it is preferred that the 
calendaring treatment is practiced at the final finishing step after 
practicing various treatments. In the calendaring treatment, known metal 
rolls and elastic rolls being used for the production of ordinary papers 
are used. 
There is no particular restriction on the thickness of the base paper as 
the support being used in the present invention but it is preferred that 
the basis weight of the base paper is from 50 g/m.sup.2 to 250 g/m.sup.2 
and the thickness thereof is from 50 .mu.m to 250 .mu.m. 
On the support being used in the present invention can be coated various 
back coatings for a static prevention, a curing prevention, etc. Also, the 
back coating layer can contain the inorganic antistatic agents, organic 
antistatic agents, hydrophilic binders, latexes, curing agents, pigments, 
surface active agents, etc., described or illustrated in JP-B-52-18020, 
JP-B-57-9059, JP-B-57-53940, JP-B-58-56859 (the term "JP-B" as used herein 
means an "examined published Japanese patent application"), 
JP-A-59-214849, JP-A-58-184144, etc., as a proper combination of them. 
The photographic support having an excellent smoothness of the surface at 
the light-sensitive silver halide emulsion coated side is preferred. The 
"smoothness" is shown by the measure of the surface roughness of the 
support. 
Then, the surface roughness of the support being used in the present 
invention is explained. As the surface roughness, the center line average 
surface roughness is used as the measure. The center line average surface 
roughness is defined as follows. That is, a part of an area SM is sampled 
on the center line from the rough curved surface, when crossed coordinate 
axes, X axis and Y axis are formed on the center line of the sampled 
portion and the axis perpendicular to the center line is defined as a Z 
axis, the value shown by the following formula is defined as the central 
line average surface roughness (SRa) and shown by a unit of .mu.m. 
##EQU1## 
The values of the center line average surface roughness and the heights of 
the projections from the center line can be obtained by measuring the area 
of 5 mm.sup.2, using, for example, a three-dimentional surface roughness 
measuring apparatus (SE-30H, trade name, manufactured by Kosaka Kenkyusho 
K.K.) with a diamond needle having a diameter of 4 .mu.m, at a cut off 
value of 0.8mm, at 20 magnifications in the horizontal direction and at 
2,000 magnification in the height direction. Also, in this case, the 
moving speed of the measuring needle is preferably about 0.5 mm/second. 
The value of the support obtained by the measurement described above is 
preferably not larger than 0.15 .mu.m, and more preferably not larger than 
0.10 .mu.m. By using the support having such a surface roughness 
(smoothness), a color pring having an excellent surface smoothness is 
obtained. 
The constitution of the photographic light-sensitive material of the 
present invention can be applied to various silver halide photographic 
materials using reflective supports. For example, the color photographic 
light-sensitive material of this invention can be constituted by coating 
at least one yellow-coloring silver halide emulsion layer, at least one 
magenta-coloring silver halide emulsion layer, and at least one 
cyan-coloring silver halide emulsion layer on a reflective support. 
In a general color photographic printing paper, a color reproduction by a 
subtractive color process can be performed by using color couplers each 
forming a dye in a complementary color relation with light sensitive to 
each silver halide emulsion layer. In a general color photographic 
printing paper, the silver halide grains in the yellow-coloring silver 
halide emulsion layer, the magenta-coloring silver halide emulsion layer, 
and the cyan-coloring silver halide emulsion layer are each spectrally 
sensitized with a blue-sensitive spectral sensitizing dye, a 
green-sensitive spectral sensitizing dye, and a red-sensitive spectral 
sensitizing dye, respectively and these silver halide emulsion layers thus 
spectrally sensitized are coated on the reflective support in this order. 
Also, in a reversal color photographic paper, the silver halide grains in 
the foregoing coloring silver halide emulsion layers in the order 
described above are each spectrally sensitized with a blue-sensitive 
spectral sensitizing dye, a green-sensitive spectral sensitizing dye, and 
a red-sensitive spectral sensitizing dye, respectively, and these emulsion 
layers are coated on a support in the order of the red-sensitive emulsion 
layer, the green-sensitive emulsion layer, and the blue-sensitive emulsion 
layer. However, other disposition order of the color-sensitive silver 
halide emulsion layers may be employed. That is, from the view point of 
quick processing, it is preferred, as the case may be, that the 
light-sensitive silver halide emulsion layer containing silver halide 
grains having the largest mean grain size is disposed as the uppermost 
layer and also from the view point of the storage stability under light 
irradiation, it is preferred, as the case may be, that the 
magenta-coloring silver halide emulsion layer is dispersed as the 
lowermost layer. 
Also, the light-sensitive silver halide emulsion layer may not have the 
foregoing correspondence with the coloring hue and further, at least one 
infrared sensitive silver halide emulsion layer may be used. Also, the 
light-sensitive silver halide emulsion layer may be composed of plural 
silver halide emulsion layers. Also, in the photographic light-sensitive 
material of the present invention, a light-insensitive layer is formed 
between the light-sensitive silver halide emulsion layer and the support, 
between the light-sensitive emulsion layer and the light-sensitive 
emulsion layer, and on upper light-sensitive emulsion layer (the farthest 
layer from the support) for various purposes such as a color mixing 
prevention, an irradiation/halation prevention, a light filter, the 
protection of the light-sensitive emulsion layer, etc. 
Also, in the case of a black and white photographic printing paper, the 
light-sensitive material is constituted by forming at least one silver 
halide emulsion layer which is spectrally sensitized or is not spectrally 
sensitized in a panchromatic or orthochromatic region on the support. 
In the silver halide photographic material of the present invention, silver 
chloride, silver bromide, silver chlorobromide, silver iodobromide, silver 
chlorobromide, silver chloroiodo-bromide, etc., can be used as the silver 
halide grains but for the purpose of quickening and simplifying 
photographic processing, a silver chlorobromide emulsion is preferred. For 
the silver chlorobromide emulsion, silver chloride grains or silver 
chlorobromide or silver chloroiodo-bromide grains having at least 95 mole 
% silver chloride can be preferably used. In particular, for quickening 
the photographic processing time, silver chlorobromide or silver chloride 
containing substantially no silver iodide. In the case, the term 
"containing substantially no silver iodide" means the content of silver 
iodide is not more than 1 mole %, and preferably not more than 0.2 mole %. 
On the other hand, for the purposes of increasing a high irradiation 
sensitivity, increasing a spectral sensitizing sensitivity, or increasing 
the stability of the photographic light-sensitive material with the 
passage of time, the high silver chloride emulsion containing from 0.01 to 
3 mole % silver iodide on the surface of the emulsion as described in 
JP-A-3-84545 is, as the case may be, preferably used. 
The halogen composition of the silver halide emulsion being used in the 
present invention may be different or same among the silver halide grains 
and when the silver halide emulsion containing silver halide grains having 
the same halogen composition among the grains is used, the property of the 
silver halide grains can be easily homogenized. Also, as to the halogen 
composition distribution in the insides of the silver halide grains, 
so-called uniform type silver halide grains wherein the halogen 
composition is same in any portions of the silver halide grains, so-called 
laminated layer type silver halide grains wherein the halogen composition 
in the core in the insides of the silver halide grains differs from the 
halogen composition in the shell (single layer or plural layers) 
surrounding the core, or the silver halide grains of the structure having 
non-layer like portions having a different halogen composition in the 
insides or the surfaces of the silver halide grains (in the case of having 
such portions on the surfaces of the silver halide grains, the structure 
that the portions having the different halogen composition join to the 
edges, the corners, or the surfaces of the silver halide grains) can be 
properly used. For obtaining a high sensitivity, the use of the latter two 
kinds of the silver halide grains is more advantageous than the case of 
using the uniform type silver halide grains and is also preferred from the 
point of the pressure resistance. 
When the silver halide grains have the structure as described above, the 
boundary portion between the portions each having a different halogen 
composition may be a clear boundary, an indistinct boundary forming mixed 
crystals by the difference of the halogen composition, or the boundary 
positively having a continuous change of structure. 
In the high-silver chloride emulsion being used in the present invention, 
the silver halide grains of the structure having the local phases of 
silver bromide in the insides and/or the surfaces of the silver halide 
grains as layer form or a non-layer form as described above are preferred. 
The halogen composition of the foregoing local phases is preferably at 
least 10 mole %, and more preferably over 20 mole % in the content of 
silver bromide. The silver bromide content of the silver bromide local 
phases can be analyzed by using an X-ray diffraction method (e.g., 
described in Shin Jikken Kagaku Koza (New Experimental Chemistry Course) 
6, "Koozou Kaiseki (Structure Analysis), published by Maruzen K.K.). 
Also, these local phases can exist in the insides of the grains, or the 
edges of, the corners of, or on the surfaces of the grains but as one of 
preferred examples, there are epitaxially grown local phases at the corner 
portions of the silver halide grains. 
Furthermore, for the purpose of reducing the replenishing amounts of the 
photographic processing liquids, it is effective to further increase the 
content of silver chloride in the silver halide emulsion. In such a case, 
the silver halide emulsion of almost pure silver chloride such as the 
silver halide content is from 98 mole % to 100 mole % is preferably used. 
The mean grain size (the diameter of the circle equivalent to the projected 
area of the grain is defined as the grain size and the mean grain size is 
the number mean value of them) of the silver halide grains contained in 
the silver halide emulsion being used in the present invention is 
preferably from 0.1 .mu.m to 2 .mu.m. 
Also, the grain size distribution of the silver halide grains is preferably 
of a so-called mono-disperse type that the coefficient of variation (the 
standard deviation of the grain size distribution divided by the mean 
grain size) is not more than 20%, preferably not more than 15%, and more 
preferably not more than 10%. In this case, for obtaining a wide latitude, 
it is preferably practiced that the foregoing so-called monodisperse 
silver halide emulsions are blended in one layer or are coated as 
multilayers. 
The form of the silver halide grains contained in the photographic silver 
halide emulsion being used in the present invention may be a regular 
crystal form such as cubic, tetradecahedral, or octahedral, an irregular 
crystal form such as spherical, tabular, etc., or a composite form 
thereof. Also, a mixture of the silver halide grains having various 
crystal forms may be used. In the present invention, the silver halide 
grains having at least 50%, preferably at least 70%, and more preferably 
at least 90% the grains having the foregoing regular crystal form are 
preferably used. 
Also, in addition to the silver halide emulsions described above, a silver 
halide emulsion containing silver halide grains wherein tabular silver 
halide grains having an average aspect ratio (circle-converted 
diameter/thickness) of at least 5, and preferably at least 8 account for 
at least 50% of the total grains can be preferably used in the present 
invention. 
The silver chloro(bromide) emulsion for use in this invention can be 
prepared using the methods described in P. Glafkides, Chimie et Physique 
Photographique, (published by Paul Montel Co., 1967), G. F. Duffin, 
Photographic Emulsion Chemistry, (published by Focal Press Co., 1966), V. 
L. Zelikman et al, Making and Coating Photographic Emulsion, (published by 
Focal Press Co., 1964), etc. 
That is, the emulsion can be prepared by an acid method, a neutralization 
method, an ammonia method, etc., and as a system of reacting a soluble 
silver salt and a soluble halide, a single jet method, a double jet 
method, or a combination thereof may be used. A so-called reverse mixing 
method of forming silver halide grains in the existence of excess silver 
ions can be also employed. As one system of the double jet method, a 
so-called controlled double jet method of keeping a constant pAg in a 
liquid phase of forming silver halide grains can be used. According to the 
method, a silver halide emulsion containing silver halide grains having a 
regular crystal form and substantially uniform grain sizes can be 
obtained. 
It is preferred that the local phases or the substrate thereof of the 
silver halide grains being used in this invention contains a foreign metal 
ion or the complex ion thereof. The preferred metal is selected from the 
ions of the metals belonging to group VIII and group IIb of the periodic 
table or the metal complexes thereof, a lead ion, and a thallium ion. For 
the local phases, the metal ion selected from iridium, rhodium, iron, 
etc., or the complex ions thereof can be mainly used as a combination 
thereof and for the substrate, the metal ion selected from osmium, 
iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, 
etc., or the complex ions thereof can be mainly used as a combination 
thereof. Also, the kind and the concentration of the metal ion(s) can be 
changed between the local phases and the substrate. These metals may be 
used as a mixture of plural kinds thereof. In particular, it is preferred 
that iron and an iridium compound exist in the local phases of silver 
bromide. 
The compounds for supplying these metal ions are contained in the local 
phases and/or other grain portions (substrate) of the silver halide grains 
for use in this invention by adding the compounds to an aqueous gelatin 
solution, which becomes a dispersion medium, an aqueous halide solution, 
an aqueous silver salt solution, or other aqueous solution at the 
formation of the silver halide or a means of adding the form of silver 
halide fine grains previously containing the metal ion(s) to the 
above-described solution and dissolving the fine grains. 
The metal ion(s) being used in this invention can be contained in the 
silver halide grains before, during, or after the formation of the silver 
halide grains. The step of adding the metal ion(s) can be changed 
according to the positions of the silver halide grains in which the metal 
ion(s) are contained. 
The silver halide emulsion being used in the present invention is usually 
subjected to a chemical sensitization and a spectral sensitization. 
As the chemical sensitizing method, a chemical sensitization using a 
chalcogen sensitizer (practically, a sulfur sensitization by the addition 
of a unstable sulfur compound, a selenium sensitization with a selenium 
compound, and a tellurium sensitization with a tellurium compound), a 
noble metal sensitization such as a gold sensitization, and a reduction 
sensitization can be used singly or as a combination thereof. 
As compounds being used for the chemical sensitization, the compounds 
described in JP-A-62-215272, pages 18, right lower column to page 22, 
right upper column are preferably used. 
The effect of the constitution of the photographic light-sensitive material 
of the present invention is more remarkable in the case of using a 
high-silver chloride emulsion subjected to a gold sensitization. 
The silver halide emulsion for use in this invention is a so-called surface 
latent image-type silver halide emulsion forming a latent image mainly on 
the surfaces of the silver halide grains. 
To the silver halide emulsions for use in this invention can be added 
various compounds or the precursors thereof for preveing the formation of 
fog during the production, the storage, and/or photographic processing of 
the photographic light-sensitive material or for stabilizing the 
photographic performance thereof. As such compounds, the compounds 
described in JP-A-62-215272, pages 39 to 72 are preferably used. 
Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds (said aryl 
reside has at least one electron attrative group) described in EP 447,647 
are also preferably used. 
The spectral sensitization is carried out for imparting a spectral 
sensitivity to the desired wavelength region of the silver halide emulsion 
of each emulsion layer of the photographic light-sensitive material of 
this invention. 
As the spectral sensitizing dyes being used for the spectral sensitizations 
of blue, green, and red regions in the photographic light-sensitive 
material of this invention, the dyes described, e.g., in F. M. Harmer, 
Heterocyclic Compounds-Cyanine Dyes and Related Compounds, (published by 
John Wiley & Sons [New York, London], 1964) can be used. 
Examples of the practical compound and the spectral sensitizing method are 
described in JP-A-62-215272 described above, page 22, right upper column 
to page 38 and they can be preferably used in this invention. Also, as a 
red-sensitive spectral sensitizing dye for silver halide grains having a 
particularly high silver chloride content, the spectral sensitizing dyes 
described in JP-A-3-123340 are very preferred from the view points of the 
stability, the strength of adsorption, the temperature reliance of light 
exposure, etc. 
In the case of spectrally sensitizing the infrared region with a good 
efficiency in the photographic light-sensitive material of the present 
invention, the sensitizing dyes described in JP-A-3-15049, page 12, left 
upper column to page 21, left lower column, JP-A-3-20730, page 4, left 
lower column to page 15, left lower column, EP 0,420,011, page 4, line 21 
to page 6, line 54, EP 0,420,012, page 4, line 12 to page 10, line 33, EP 
0,443,466, and U.S. Pat. No. 4,975,362 are preferably used. 
For incorporating these spectral sensitizing dyes in the silver halide 
emulsion, they may be directly dispersed in the emulsion or may be added 
as a solution thereof in a solvent such as water, methanol, ethanol, 
propanol, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, etc., or a mixed 
solvent thereof. Also, the spectral sensitizing dye may be added to the 
silver halide emulsion as an aqueous solution thereof containing an acid 
or a base as described in JP-B-44-23389, JP-B-44-27555, JP-B-57-22089, 
etc., (the term "JP-B" as used herein means an "examined published 
Japanese patent application") or may be added to the emulsion as an 
aqueous solution or a colloid dispersion thereof containing a surface 
active agent as described in U.S. Pat. Nos. 3,822,135 and 4,006,025. Also, 
after dissolving the spectral sensitizing dye in a solvent substantially 
immiscible with water, such as phenoxy ethanol, etc., the solution is 
dispersed in water or a hydrophilic colloid and the dispersion may be 
added to the emulsion. Furthermore, the spectral sensitizing dye is 
directly dispersed in a hydrophilic colloid and the dispersion may be 
added to the emulsion as described in JP-A-53-102733 and JP-A-58-105141. 
The time for adding the dye to the emulsion may be any step in the 
preparation of the emulsion, which is known to be useful. That is, the 
time for adding the dye can be selected from the steps of before and 
during the formation of the silver halide emulsion, the step of from 
directly after the formation of the silver halide grains to just before 
the water-washing step, the steps of before and during the chemical 
sensitization of the emulsion, the steps of from directly after the 
chemical sensitization to caking the emulsion by cooling, and the step of 
preparing the coating liquid of the emulsion. Usually, the addition of the 
dye is performed after finishing the chemical sensitization before coating 
the emulsion. Also, the spectral sensitizing dye is added to the emulsion 
together with a chemical sensitizer and the spectral sensitization and the 
chemical sensitization can be carried out simultaneously as described in 
U.S. Pat. Nos. 3,628,969 and 4,225,666, the spectral sensitization can be 
performed before the chemical sensitization as described in 
JP-A-58-113928, and also the spectral sensitizing dye may be added before 
finishing the formation of the precipitates of the silver halide grains to 
initiate the spectral sensitization. 
Furthermore, as described in U.S. Pat. No. 4,225,666, a part of the 
spectral sensitizing dye is added before the chemical sensitization and 
the residue of the dye can be added after the chemical sensitization and 
further, the method described in U.S. Pat. No. 4,183,756 can be used and 
the addition of the dye may be any step during the formation of silver 
halide grains. 
In these steps, it is particularly preferred to add the sensitizing dye 
before water-washing step of the emulsion or before the chemical 
sensitization of the emulsion. 
The addition amount of the spectral sensitizing dye is in a wide range and 
is in the range of preferably from 0.5.times.10.sup.-6 mole to 
1.0.times.10.sup.-2 mole, and more preferably from 1.0.times.10.sup.-6 
mole to 5.0.times.10.sup.-3 mole per mole of the silver halide. 
In the case of using the sensitizing dyes having spectral sensitizing 
sensitivities in a red region to an infra red region in the present 
invention, it is particularly preferred to use the dyes together with the 
compounds described in JP-A-2-157749, page 13, right lower column to page 
22, right lower column. By using these compounds, the storage stability of 
the photographic light-sensitive material, the stability of processing, 
and the supersensitization effect can be greatly increased. In the 
foregoing compounds, the use of the compounds shown by the formulae (IV), 
(V) and (VI) in the above patent publication is particularly preferred. 
The compound is used in an amount of from 0.5.times.10.sup.-5 mole to 
5.0.times.10.sup.-2 mole, and preferably from 5.0.times.10.sup.-5 mole to 
5.0.times.10.sup.-3 mole per mole of the silver halide and also the 
advantageous using amount of the compound is in the range of from 0.1 
times to 10,000 times, and preferably 0.5 times to 5,000 times per mole of 
the sensitizing dye. 
The photographic light-sensitive material of the present invention is 
preferably used for a digital scanning light exposure using a 
monochromatic high-density light such as a gas laser, a light emitting 
diode, a semiconductor laser, or a second high-harmonic generating source 
(SHG) combining a semiconductor laser or a solid state laser using a 
semiconductor laser as the excitation light source and a nonlinear optical 
crystal in addition to the use for the printing system using an ordinary 
negative printer. For making the system compact and low cost, it is 
preferred to use a semiconductor laser or the second high-harmonic 
generating light source (SHG) combining a semiconductor laser or a solid 
state laser and a nonlinear optical crystal. In particular, for designing 
an apparatus which is compact, is low cost, has a longer life, and has a 
high stability, the use of a semiconductor laser is preferred and also it 
is desirable to use a semiconductor laser as one of the exposure light 
sources. 
In the case of using such a scanning exposure light-source, the spectral 
sensitivity maximum of the photographic light-sensitive material of the 
present invention can be optionally selected according to the wavelength 
of the scanning exposure light source being used. Since in the SHG light 
source obtained by combining a solid state laser using a semiconductor 
laser as the exciting light source or a semiconductor laser and a 
nonlinear optical crystal, the oscillation wavelength of laser can be 
shortened to a half thereof, a blue light or a green light is obtained. 
Accordingly, it is possible to give the spectral sensitivity maximum of 
the photographic light-sensitive material in the ordinary three regions of 
blue, green, and red. For using a semiconductor laser as the light source 
for making the apparatus low cost, highly stable, and compact, it is 
preferred that at least two emulsion layers of the photographic 
light-sensitive material have the spectral sensitivity maximum for at 
least 670 nm. This is because the light emitting wavelength regions of 
inexpensive and stable group III-V series semiconductor lasers available 
at present and being low cost are in the regions of from red to infrared 
only. However, in an experimental level, the oscillation wavelength 
regions in green and blue regions of group II-VI series semiconductor 
lasers have been confirmed and when the production technique of 
semiconductor lasers is developed, it is sufficiently anticipated that 
these semiconductor lasers is used stably and at a low cost. In such a 
case, the necessity that at least two emulsion layers of the photographic 
light-sensitive material having the spectral sensitivity maximum at least 
670 nm becomes less. 
In such a scanning exposure, the time of exposing the silver halide in a 
photographic light-sensitive material is a time required for exposing a 
fine area thereof. As the fine area, the minimum unit of controlling the 
light intensity from each digital datum is generally used and is called as 
a pixel. Therefore, according to the size of the pixel, the exposure time 
per one pixel is changed. The size of the pixel depends on the pixel 
density and the actual range is from 50 to 2,000 dpi. When the exposure 
time is defined as the time for exposing the pixel size in the case that 
the pixel density is 400 dpi, the exposure time is preferably not longer 
than 10.sup.-4 second, and more preferably not longer than 10.sup.-6 
second. 
In the photographic light-sensitive material of the present invention, it 
is preferred to color the hydrophilic colloid layer for the purpose of 
preventing the irradiation and halation and of improving the safelight 
safety, etc. The compound of the general formula (I) being used in this 
invention can be also used as a coloring material and hence it is 
preferred to use the compound for the purposes of coloring and improving 
the pressure resistance. Also, as a water-soluble dye being used together 
with the foregoing compound of the general formula (I), there are the dyes 
(in particular, oxonol dyes and cyanine dyes) capable of being decolored 
by processing described in EP 0,337,490A2, pages 27 to 76. 
Some of these water-soluble dyes deteriorate the color separation and the 
safelight safety if the using amount thereof is increased. As the dyes 
which can be used without deteriorating the color separation, there are 
the water-soluble dyes described in EP 0,539,978A1, Japanese Patent 
Application Nos. 3-310189 and 3-310039 and as the case may be, the use of 
the water-soluble dye together with the compound of this invention is 
preferred. 
In the case of applying such coloring, the coloring material diffuses 
regardless the position of the added layer of the coloring material and 
diffuses in the whole layers constituting the photographic light-sensitive 
material. The coloring density is at least 0.2, preferably at least 0.3, 
and more preferably at least 0.5 at the light intensity maximum wavelength 
of the light source being used for the light exposure. In particular, it 
is preferred that the density of the absorption maximum of the colored 
range colored using the compound of this invention is at least 0.3. 
In the present invention, the colored layer with the compound of this 
invention in place of the foregoing water-soluble dye or together with the 
water-soluble dye, said colored layer capable of being decolored in 
processing, is used. The colored layer capable of being decolored in 
processing, which is used in this invention, may be in directly contact 
with the silver halide emulsion layer or disposed in contact with the 
emulsion layer through an interlayer containing a processing color mixing 
inhibitor such gelatin and hydroquinone. It is preferred that the colored 
layer is disposed under (the support side) the silver halide emulsion 
layer coloring to the same kind of an elementary color as the colored 
color. Colored layers each corresponding to all elementary colors or may 
be disposed and colored layers each corresponding to a part of an 
optionally selected color may be also disposed. Further colored layers 
each corresponding to plural elementary colors may be disposed. 
As to the optical reflective density of each of these colored layers, in 
the wavelength region to be used for exposure (a visible light region of 
from 400 nm to 700 nm in an ordinary printer exposure and the wavelength 
of the scanning exposure light source being used in the case of scanning 
exposure), the optical density at the wavelength of the highest optical 
density is preferably from 0.2 to 3.0, more preferably from 0.5 to 2.5, 
and particularly preferably from 0.8 to 2.0. 
For forming the colored layer(s), a conventionally known method can be 
used. For example, there are a method of incorporating in a hydrophilic 
colloid layer as state of a solid fine particle dispersion as is seen in 
the dye described in JP-A-2-282244, page 3, right upper column to page 8 
or the dye described in JP-A-3-7931, page 3, right upper column to page 
11, left lower column, a method of mordanting a cation polymer with an 
anionic dye, a method of adsorbing a dye to the fine grains of a silver 
halide, etc., to fix the fine grains in the layer, and a method of using 
colloid silver as described in JP-A-1-239544. 
As a method of dispersing the fine powder of a dye in a solid state, for 
example, a method of incorporating a fine-powdery dye which is 
substantially water-insoluble at pH of lower than 6 but is substantially 
water-soluble at pH of at least 8 is described in JP-A-2-308244, pages 4 
to 13. Also, a method of mordanting a cation polymer with an anionic dye 
is described in JP-A-2-84637, pages 18 to 26. A method of preparing 
colloidal silver as a light absorbent is described in U.S. Pat. Nos. 
2,688,601 and 3,459,563. Also, the use of tabular thin colloid silver 
particles having a thickness of thinner than 20 nm described in 
JP-A-5-134358 is preferred. 
In the methods described above, the method of incorporating the fine 
powdery dye and the method of using colloid silver are preferred in this 
invention. 
As a binder or a protective colloid which can be used for the photographic 
light-sensitive material of this invention, gelatin is advantageously used 
but other hydrophilic colloid can be used singly or together with gelatin. 
As preferred gelatin, low-calcium gelatin having a calcium content of not 
more than 800 ppm, and more preferably not more than 200 ppm is used. 
Also, for preventing the growth of various fungi and bacteria growing in 
the hydrophilic colloid layers to deteriorate the image quality, it is 
preferred to add the antifungal agents described in JP-A-63-271247. 
At printer exposing the photographic light-sensitive material of the 
present invention, it is preferred to use the hand stop filter described 
in U.S. Pat. No. 4,880,726, whereby color mixing is removed and the color 
reproducibility is greatly improved. 
The image-exposed color photographic light-sensitive material of this 
invention can be subjected to conventional color photographic processing 
but in the case of the color photographic light-sensitive material of this 
invention, it is preferred for the purpose of quick processing to subject 
the color photographic material to a blix (bleach-fix) processing after a 
color development. In particular, in the case of using the high-silver 
chloride emulsion(s) described above, pH of the blix solution is 
preferably lower than about 6.5, and more preferably lower than about 6 
for the purpose of the desilvering acceleration, etc. 
The silver halide emulsions and other elements (additives, etc.) being used 
for the photographic light-sensitive materials of this invention, the 
layers (disposition of layers, etc.) for constituting the photographic 
light-sensitive materials, and the processing methods and additives for 
processing the light-sensitive materials of this invention described in 
the following patent publications, in particular, EP 0,355,660A2 
(JP-A-2-139544) are preferably used. 
__________________________________________________________________________ 
Photographic 
elements 
JP-A-62-215292 
JP-A-2-33144 EP 0,355,660A2 
__________________________________________________________________________ 
Silver halide 
pp. 10, right upper colmn, 
pp. 28, right upper colmn, 
pp. 45, line 53 to pp. 47, 
emulsion 
line 6 to pp. 12, left 
line 16 to pp. 29, right 
line 3, and 
lower colmn, line 5, and 
lower colmn, line 11, and 
pp. 47, lines 20 to 22. 
pp. 12, right lower colmn, 
pp. 30, lines 2 to 5. 
line 4 from bottom to pp. 13, 
left upper colmn, line 17. 
Silver halide 
pp. 12, left lower colmn, 
-- -- 
solvent lines 6 to 14, and pp. 13, 
left upper colmn, line 3 
from bottom to pp. 18, left 
lower colmn, last line. 
Chemical 
pp. 12, left lower colmn, 
pp. 29, right lower colmn, 
pp. 47, lines 4 to 9. 
sensitizer 
line 3 from bottom to 
line 12 to last line. 
right lower colmn, line 
5 from bottom, and pp. 18, 
right lower colmn, line 
1 to pp. 22, right upper 
colmn, line 9 from bottom. 
Spectral 
pp. 22, right upper colmn, 
pp. 30, left upper colmn, 
pp. 47, lines 10 to 15. 
sensitizer 
line 8 from bottom to 
lines 1 to 13. 
(spectral 
pp. 38, last line. 
sensitizing 
process) 
Emulsion 
pp. 39, left upper colmn, 
pp. 30, left upper colmn, 
pp. 47, lines 16 to 19. 
stabilizer 
line 1 to pp. 72, right 
line 14 to right upper 
upper colmn, last line. 
colmn, line 1. 
Develop- 
pp. 72, left lower colmn, 
-- -- 
ment line 1 to pp. 91, right 
acceler- 
upper colmn, line 3. 
ator 
Color coupler 
pp. 91, right upper colmn, 
pp. 3, right upper colmn, 
pp. 4, lines 15 to 27, 
(cyan, line 4 to pp. 121, left 
line 14 to pp. 18, left 
pp. 5, line 30 to pp. 28, 
magenta upper colmn, line 6. 
upper colmn, last line, 
last line, pp. 45, lines 
and yellow and pp. 30, right upper 
29 to 31, and pp. 47, 
couplers) colmn, line 6 to pp. 35 
line 23 to pp. 63, line. 
right lower colmn, line 11. 
50 
Color form- 
pp. 121, left lower colmn, 
-- -- 
ing accel- 
line 7 to pp. 125, right 
erator upper colmn, line 1. 
UV absorber 
pp. 125, right upper colmn, 
pp. 37, right lower colmn, 
pp. 65, lines 22 to 31. 
line 2 to pp. 127, left 
line 14 to pp. 38, left 
lower colmn, last line. 
upper colmn, line 11. 
Anti-fading 
pp. 127, right lower colmn, 
pp. 36, right upper colmn, 
pp. 4, line 30 to pp. 5, 
agent line 1 to pp. 137, left 
line 12 to pp. 37, left 
line 23, pp. 29, line 1 
(an image 
lower colmn, line 8. 
upper colmn, line 19. 
to pp. 45, line 25, 
stabilizer) pp. 45, lines 33 to 40, 
and pp. 65, lines 2 to 
21. 
High boiling 
pp. 137, left lower colmn, 
pp. 35, right lower colmn, 
pp. 64, lines 1 to 51. 
and/or low 
line 9 to pp. 144, right 
line 14 to pp. 36, left 
boiling upper, last line. 
upper, line 4 from bottom. 
organic 
solvent 
Process for 
pp. 144, left lower colmn, 
pp. 27, right lower colmn, 
pp. 63, line 51 to pp. 
dispersing 
line 1 to pp. 146, right 
line 10 to pp. 28, left 
64, line 56. 
photograph- 
upper colmn, line 7. 
upper, last line, and 
ic additives pp. 35, right lower colmn, 
line 12 to pp. 36, right 
upper colmn, line 7. 
Hardener 
pp. 146, right upper colmn, 
-- -- 
line 8 to pp. 155, left 
lower colmn, line 4. 
Precursor of 
pp. 155, left lower colmn, 
-- -- 
a develop- 
line 5 to right lower 
ing agent 
colmn, line 2. 
Develop- 
pp. 155, right lower colmn, 
-- -- 
ment inhib- 
lines 3 to 9. 
itor-releas- 
ing compound 
Light- pp. 156, left upper colmn, 
pp. 28, right upper colmn, 
pp. 45, lines 41 to 52 
sensitive 
line 15 to right lower 
lines 1 to 15. 
layer colmn, line 14. 
structure 
Dye pp. 156, right lower colmn, 
pp. 38, left upper colmn, 
pp. 66, lines 18 to 22. 
line 15 to pp. 184, right 
line 12 to right upper 
lower colmn, last line. 
colmn, line 7. 
Anti-color 
pp. 185, left upper colmn, 
pp. 36, right upper colmn, 
pp. 64, line 57 to pp. 65 
mixing line 1 to pp. 188, right 
lines 8 to 11. 
line 1. 
agent lower colmn, line 3. 
Gradation 
pp. 188, right lower colmn, 
-- -- 
controller 
lines 4 to 8. 
Anti-stain 
pp. 188, right lower colmn, 
pp. 37, left upper colmn, 
pp. 65, line 32 to pp. 
agent line 9 to pp. 193, right 
last line to right lower 
66, line 17. 
lower colmn, line 10. 
colmn, line 13. 
Surface pp. 201, left lower colmn, 
pp. 18, right upper colmn, 
-- 
active line 1 to pp. 210, right 
line 1 to pp. 24, right 
agent upper colmn, last line 
lower colmn, last line, 
and pp. 27, left lower 
colmn, line 10 from 
bottom to right lower 
colmn, line 9. 
Fluorinat- 
pp. 210, left lower colmn, 
pp. 25, left upper colmn, 
-- 
ed compound 
line 1 to pp. 222, left 
line 1 to pp. 27, right 
(anti-static 
lower colmn, line 5. 
lower colmn, line 9. 
agent, coating 
aid, lubricant 
and anti-adhe- 
sion agent) 
Binder pp. 222, left lower colmn, 
pp. 38, right upper colmn, 
pp. 66, lines 23 to 28. 
(hydrophilic 
line 6 to pp. 225, left 
lines 8 to 18. 
colloid) 
upper colmn, last line 
Thickener 
pp. 225, right upper colmn, 
-- -- 
line 1 to pp. 227, right 
upper colmn, line 2. 
Anti-static 
pp. 227, right upper colmn, 
-- -- 
agent line 3 to pp. 230, left 
upper colmn, line 1. 
Polymer pp. 230, left upper colmn, 
-- -- 
latex line 2 to pp. 239, last line 
Matting pp. 240, left upper colmn, 
-- -- 
agent line 1 to right upper 
colmn, last line. 
Photo- pp. 3, right upper colmn, 
pp. 39, left upper colmn, 
pp. 67, line 14 to pp. 
graphic line 7 to pp. 10, right 
line 4 to pp. 42, left 
69, line 28. 
process- 
upper colmn, line 5. 
upper colmn, last line. 
ing method 
(processing 
steps and 
additives) 
__________________________________________________________________________ 
Remarks: 
1. The content amended according to the Amendment of March 16, 1987 is 
included in the cited items of JPA-62-215272. 
2. Of the above color couplers, also preferably used as a yellow coupler 
are the socalled short wave type yellow couplers described in 
JPA-63-231451, JPA-63-123047, JPA-63-241547, JPA-1-173499, JPA-1-213648, 
and JPA-1-250944. 
Also, as the color couplers described above, the so-called short wave-type 
yellow couplers described in JP-A-63-231451, JP-A-63-123047, 
JP-A-63-241547, JP-A-1-173499, JP-A-1-213648, and JP-A-1-250944 are 
preferably used. 
It is preferred that each of the cyan, magenta, and yellow couplers is 
impregnated in a loadable latex polymer (e.g., U.S. Pat. No. 4,203,716) in 
the presence (or absence) of the high-boiling organic solvent described in 
the above table or is dissolved together with a polymer which is 
water-insoluble and organic solvent-soluble, and emulsion-dispersed in an 
aqueous hydrophilic colloid solution. 
As the water-insoluble and organic solvent-soluble polymer being preferably 
used in the present invention, there are the homopolymers and the 
copolymers described in U.S. Pat. No. 4,857,449, columns 7 to 15 and PCT 
WO 88/00723, pages 12 to 30. Methacrylate series or acrylamide series 
polymer is more preferred and acrylamide polymer is most preferred. 
For the photographic light-sensitive material of the present invention, it 
is preferred to use the color image storage stability improving compound 
as described in EP 0,277,589A2 together with the couplers. It is 
particularly preferred to use the foregoing compound together with a 
pyrazoloazole coupler or a pyrrolotriazole coupler. 
That is, the use of the compound forming a chemically inactive and 
substantially colorless compound by chemically combining with an aromatic 
amine developing agent remaining after color developing processing 
described in the foregoing patent specification and/or the compound 
forming a chemically inactive and substantially colorless compound by 
chemically combining with the oxidation product of an aromatic amine 
developing agent remaining after color developing processing singly or 
simultaneously is preferred for preventing the formation of stains and the 
occurrence of other side actions by the formation of colored dyes by the 
reaction of couplers and the color developing agent or the oxidation 
product thereof remaining in the emulsion layers during storing the color 
images formed after processing. 
Also, as the cyan coupler, the use of the diphenylimidazole type cyan 
couplers described in JP-A-2-33144 as well as the 3-hydroxypyridine type 
cyan couplers described in EP 0,333,185A2 (in particular, the 
two-equivalent coupler formed by bonding a chlorine releasing group to the 
four-equivalent coupler (42) illustrated therein, or the coupler (6) or 
(9) is preferred), the cyclic active methylene type cyan couplers 
described in JP-A-64-32260 (in particular, couplers 3, 8, and 34 
illustrated therein as practical examples are particularly preferred), the 
pyrrolopyrazole type cyan couplers described in EP 0,456,226A1, the 
pyrroloimidazole type cyan couplers described in EP 0,484,909, and the 
pyrrolotriazole type cyan couplers described in EP 0,488,248 and EP 
0,491,197A1 is preferred. In these cyan couplers, the use of the 
pyrrolotriazole type cyan couplers is particularly preferred. 
As the yellow coupler, in addition to the compounds described in the above 
table, the acrylacetamide type yellow couplers having a 3 to 5 membered 
cyclic structure at the acyl group described in EP 0,447,969A1, the 
malondianilido type yellow couplers having a cyclic structure described in 
EP 0,482,552A1, and the acylacetamido type yellow couplers having a 
dioxane structure described in U.S. Pat. No. 5,118,599 are preferably 
used. In these couplers, the use of the acylacetamide type yellow couplers 
wherein the acyl group is a 1-alkylcyclopropane-1-carbonyl group and the 
malondianilido type yellow couplers wherein one of the anilides 
constitutes an indoline ring is particularly preferred. These couplers can 
be used singly or as a combination thereof. 
As the magenta coupler being used in the present invention, the 
5-pyrazolone series magenta couplers and the pyrazoloazole series magenta 
couplers as described in the known literature in the above table are used 
but in the points of the hue, the color image stability, coloring 
property, etc., the use of the pyrazolotriazole couplers wherein a 
secondary or tertiary alkyl group is directly bonded to the 2, 3, or 
6-position of the pyrozolotriazole ring as described in JP-A-61-65245, the 
pyrazoloazole couplers having a sulfonamido group in the molecule as 
described in JP-A-61-65246, the pyrazoloazole couplers having an 
alkoxyphenylsulfonamido ballast group as described in JP-A-61-147254, and 
the pyrazoloazole couplers having an alkoxy group or an aryloxy group at 
the 6-position thereof as described in EP 0,226,849A and EP 0,294,785A is 
preferred. 
For the processing process of the color photographic light-sensitive 
materials of the present invention, in addition to the processes described 
in the above table, the use of the processing materials and the processing 
processes described in JP-A-2-207250, page 26, right lower column, line 1 
to page 34, right upper column, line 9 and JP-A-4-97355, page 5, left 
upper column, line 17 to page 18, right lower column, line 20 is preferred 
.

Then, the present invention is described more practically by the following 
examples. 
SYNTHESIS EXAMPLE 1 
Synthesis of 3-ethoxycarbonyl-5-hydroxypyrazole: 
To 400 ml of ethanol were added 20.6 g (0.30 mole) of hydrazine 
hydrochloride and 63.0 g (0.33 mole) of sodium oxalacetate and after 
stirring the mixture for 2 hours at room temperature, the mixture was 
refluxed for 3 hours with stirring. After distilling off methanol, 100 ml 
of water was added to the residue followed by stirring for one hour at 
room temperature. Crystals formed were recovered by filtration and washed 
with water. 
The amount of the product was 30.2 g (65% in yield). The melting point was 
from 180.degree. to 182.degree. C. 
Synthesis of Compound A-1: 
To 20 ml of methanol was added 15.6 g (0.10 mole) of 
3-ethoxycarbonyl-5-hydroxypyrazole and after adding thereto 30 ml of 40% 
methanol solution of methylamine, the mixture was stirred in an autoclave 
for 9 hours at 100.degree. C. After cooling the reaction mixture to room 
temperature, the reaction mixture was neutralized with concentrated 
hydrochoric acid and crystals formed were recovered by filtration. The 
amount of the product was 11.6 g (82% in yield). The melting point was 
238.degree. C. (decomp.) 
SYNTHESIS EXAMPLE 2 
Synthesis of 3-ethoxycarbonyl-5-hydroxy-1-methylpyrazole: 
To 800 ml of ethanol were added 108 g (1.1 mole) of sulfuric acid, 92.1 g 
(2.0 moles) of methylhydrazine, and 462.4 g (2.2 moles) of sodium 
oxalacetate and after stirring the mixture for 2 hours at room 
temperature, the mixture was refluxed for 3 hours with stirring. After 
distilled off ethanol, 800 ml of water was added to the residue and the 
mixture was allowed to stand overnight at room temperature. Crystals 
formed were recovered by filtration and washed with water. 
The amount of the product was 279 g (82% in yield). The melting point was 
151.degree. to 153.degree. C. 
Synthesis of Compound A-2: 
A mixture of 8.5 g (0.05 mole) of 
3-ethoxycarbonyl-5-hydroxy-1-methylpyrazole and 30 ml of 40% methanol 
solution of methylamine was stirred in an autoclave for 8 hours at 
100.degree. C. After cooling the reaction mixture to room temperature, the 
product was neutralized with concentrated hydrochloric acid and crystals 
formed were recovered by filtration. The amount of the product was 6.9 g 
(89% in yield). The melting point was 204.degree. to 206.degree. C. 
SYNTHESIS EXAMPLE 3 
Synthesis of Compound A-4: 
A mixture of 46.8 g (0.30 mole) of 3-ethoxycarbonyl-5-hydroxypyrazole and 
150 ml of pyrrolidine was refluxed for 18 hours with stirring. After 
cooling the reaction mixture to room temperature, 100 ml of water was 
added thereto and the product was neutralized to pH 5 with concentrated 
hydrochloric acid. Crystals formed were recovered by filtration and washed 
with an aqueous sodium chloride solution. The amount of the product was 
46.2 (85% in yield). The melting point was 280.degree. to 289.degree. C. 
SYNTHESIS EXAMPLE 4 
Synthesis of Compound C-1: 
To 15.6 g (0.10 mole) of 3-ethoxycarbonyl-5-hydroxypyrazole was added 35 ml 
(0.40 mole) of morpholine and the mixture was stirred in a nitrogen gas 
atmosphere for 12 hours at 130.degree. C. while removing ethanol formed. 
After removing excessive morpholine under reduced pressure, 30 ml of a 
saturated aqueous sodium chloride solution was added to the reaction 
mixture and pH thereof adjusted to 4 with concentrated hydrochloric acid. 
Crystals formed were recovered by filtration and washed with a saturated 
aqueous sodium chloride solution. The amount of the product was 15.4 g 
(79% in yield). The melting point was 220.degree. C. (decomp.). 
SYNTHESIS EXAMPLE 5 
Synthesis of Compound C-2: 
To 117 ml (1.32 moles) of morpholine was added 56.7 g (0.33 mole) of 
3-ethoxycarbonyl-5-hydroxy-1-methylpyrazole and the mixture was stirred in 
a nitrogen gas atmosphere for 18 hours at 130.degree. C. while removing 
ethanol formed. After distilling off excessive morpholine under reduced 
pressure, 100 ml of a saturated aqueous sodium chloride solution was added 
thereto and pH was adjusted to 4 with concentrated hydrochloric acid. 
Crystals formed were recovered by filtration and washed with a saturated 
aqueous sodium chloride solution. The amount of the product was 58.1 g 
(82% in yield). The melting point was 172.degree. to 174.degree. C. 
Compound A-3, Compound A-5, Compound C-3, and Compound C-4 can be 
synthesized by the same manners as above. 
SYNTHESIS EXAMPLE 6 
Synthesis of Compound 106: 
After mixing 3.4 g (24 mmoles) of Compound A-2 and 3.0 g (11.4 mmoles) of 
malonaldehydedianyl with 30 ml of dimethylformamide (DMF), 5 ml of 
triethylamine was further added to the mixture and the mixture was stirred 
for 4 hours at 50.degree. C. After cooling the reaction mixture to room 
temperature, 4.7 g of potassium acetate was added thereto and crystals 
formed were recovered by filtration and washed with isopropanol. The 
amount of the product was 3.4 g (80% in yield). .lambda..sub.max 534 nm 
(H.sub.2 O). 
SYNTHESIS EXAMPLE 7 
Synthesis of Compound 108: 
After mixing 5.44 g (30 mmoles) of Compound A-4 and 3.33 g (15 mmoles) of 
malonaldehydedianyl with 27 ml of acetonitrile, 5 ml of triethylamine was 
further added to the mixture and the mixture was stirred for 4 hours at 
60.degree. C. After cooling the reaction mixture to room temperature, 25 
ml of 15% methanol solution of potassium acetate and 20 ml of isobutanol 
was further added thereto. Crystals precipitated were recovered by 
filtration and washed with isobutanol. The amount of the product was 4.1 g 
(63% in yield). .lambda..sub.max 531 nm (H.sub.2 O). 
SYNTHESIS eXAMPLE 8 
Synthesis of Compound 111: 
After mixing 3.94 g (20 mmoles) of Compound C-1 and 1.48 g (10 mmoles) of 
ethyl orthoformate with 16 ml of methanol, 2 ml of triethylamine and 1 ml 
of acetic acid were further added thereto and the mixture was refluxed for 
6 hours. After cooling the reaction mixture to room temperature, 2.0 g of 
potassium acetate was added and further 20 ml of isobutanol was added 
thereto. Crystals precipitated were recovered by filtration and washed 
with isobutanol. The amount of the product was 2.11 g (48% in yield). 
.lambda..sub.max 450 nm (H.sub.2 O). 
SYNTHESIS EXAMPLE 9 
Synthesis of Compound 112: 
After mixing 4.22 g (20 mmoles) of Compound C-2 and 1.48 g (10 mmoles) of 
ethyl orthoformate with 16 ml of methanol, 2 ml of triethylamine and 1 ml 
of acetic acid were added thereto and the mixture was refluxed for 6 
hours. After cooling the reaction mixture to room temperature, 2.0 g of 
potassium acetate was added and further 20 ml of isobutanol was added 
thereto. Crystals precipitated were recovered by filtration and washed 
with isobutanol. The amount of the product was 2.74 g (55% in yield). 
.lambda..sub.max 453 nm (H.sub.2 O). 
SYNTHESIS EXAMPLE 10 
Synthesis of Compound 3: 
After mixing 3.94 g (20 mmoles) of Compound C-1 and 1.98 g (13 mmoles) of 
1,3,3-trimethoxy-1-propene with 16 ml of methanol, 2 ml of triethylamine 
and 1 ml of acetic acid were further added thereto and the mixture was 
refluxed for 6 hours. After cooling the reaction mixture to room 
temperature, 2.0 g of potassium acetate was added and 20 ml of isobutanol 
was further added thereto. Crystals precipitated were recovered by 
filtration and washed with isobutanol. The amount of the product was 2.64 
g (56% in yield). .lambda..sub.max 532 nm (H.sub.2 O). 
SYNTHESIS EXAMPLE 11 
Synthesis of Compound 118: 
After mixing 4.22 g (20 mmoles) of Compound C-2 and 2.22 g (10 mmoles) of 
malonaldehydodianyl with 10 ml of DMF, 2 ml of triethylamine was further 
added thereto and the mixture was stirred for 3 hours at 60.degree. C. 
After cooling the reaction mixture to room temperature, 2.0 g of potassium 
acetate was added and 20 ml of isobutanol was further added thereto. 
Crystals precipitated were recovered by filtration and washed with 
isobutanol. The amount of the product was 3.64 g (73% in yield). 
.lambda..sub.max 532 nm (H.sub.2 O). 
SYNTHESIS EXAMPLE 12 
Synthesis of Compound 6: 
After mixing 4.82 g (20 mmoles) of Compound C-4 and 2.22 g (10 mmoles) of 
malonaldehydodianyl with 10 ml of DMF, 2 ml of triethylamine was further 
added thereto and the mixture was stirred for 3 hours at 60.degree. C. 
After cooling the reaction mixture to room temperature, 2.0 g of potassium 
acetate was added and 20 ml of isobutanol was further added thereto. 
Crystals precipitated were recovered by filtration and washed with 
isobutanol. The amount of the product was 3.52 g (63% in yield). 
.lambda..sub.max 531 nm (H.sub.2 O). 
SYNTHESIS EXAMPLE 13 
Synthesis of Compound 115: 
After mixing 3.94 g (20 mmoles) of Compound C-1 and 2.85 g (10 m moles) of 
glutaconaldehydodianyl hydrochloride with 10 ml of methanol, 3.4 ml (24 
mmoles) of triethylamine was added thereto and the mixture was stirred for 
5 hours at 50.degree. C. After cooling the reaction mixture to room 
temperature, 2.0 g of potassium acetate and 10 ml of methanol were added 
thereto. Inorganic salts precipitated were filtered off. The filtrate 
obtained was concentrated, 20 ml of isobutanol was added thereto, and 
crystals precipitated were recovered by filtration and washed with 
isobutanol. The amount of the product was 2.81 g (57% in yield). 
.lambda..sub.max 624 nm (H.sub.2 O). 
SYNTHESIS EXAMPLE 14 
Synthesis of Compound 116: 
After mixing 4.22 g (20 mmoles) of Compound C-2 and 2.22 g (10 mmoles) of 
glutaconaldehydrodianyl with 10 ml of methanol, 3.4 ml (24 mmoles) of 
triethylamine was added thereto and the mixture was stirred for 5 hours at 
50.degree. C. After cooling the reaction mixture to room temperature, 2.0 
g of potassium acetate and 10 ml of methanol were added thereto and 
inorganic salts precipitated were filtered off. The filtrate was 
concentrated, 20 ml of isobutanol was added to the residue, and crystals 
precipitated were recovered by filtration and washed with isobutanol. The 
amount of the product was 1.72 g (33% in yield). .lambda..sub.max 626 nm 
(H.sub.2 O). 
EXAMPLE 1 
An aqueous 1% dye solution was added to an aqueous 10% gelatin solution and 
the mixture was adjusted such that when the mixture was coated at 80 
g/m.sup.2, the optical density became 1.0. To the mixture was added a 
hardening agent in an amount of 2.6% to gelatin. The liquid thus prepared 
was coated on a polyester film base having a subbing layer and after 
drying for 24 hours at 50.degree. C., the coated film was cut into a 
rectangle of 10 cm.times.12 cm to provide a sample piece. 
The sample was washed with running water for 60 seconds at 25.degree. C. 
and dried. The densities of 5 points of each sample were obtained before 
and after processing using a Macbeth transmittance densitometer TD-504 and 
the average value thereof was defined as the density. The results are 
shown in Table 1. 
As is clear from the results shown in Table 1 below, the dyes of this 
invention show the excellent decoloring property. 
TABLE 1 
______________________________________ 
Dye Before Processing 
After Processing 
______________________________________ 
9 1.00 0.05 
109 1.00 0.06 
112 0.99 0.02 
3 1.00 0.02 
11 1.00 0.03 
6 1.02 0.04 
116 1.01 0.02 
Comparative dye 1 
0.98 0.14 
Comparative dye 2 
0.99 0.18 
Comparative dye 3 
1.01 0.92 
Comparative dye 4 
1.00 0.11 
No addition 0.02 0.02 
Comparative Dye 1 
##STR28## 
Comparative Dye 2 
##STR29## 
Comparative Dye 3 
##STR30## 
Comparative Dye 4 
##STR31## 
Hardner 
##STR32## 
______________________________________ 
EXAMPLE 2 
(Preparation of Support) 
To low-density polyethylene (MRF=3) was added titanium dioxide at the ratio 
shown in Table 2 below and also zinc stearate was added thereto at a ratio 
of 3.0% by weight to the amount of titanium dioxide. After kneading the 
polyethylene together with ultramarine blue (DV-1, trade name, made by 
Daiichi Kasei Kogyo K.K.) in a banbury mixer, the mixture was formed to 
pellets to provide a masterbatch. The size of titanium dioxide measured by 
an electronmicroscope was from 0.15 .mu.m to 0.35 .mu.m and aluminum oxide 
hydrate was coated on titanium dioxide in an amount of 0.75% by weight to 
titanium dioxide as Al.sub.2 O.sub.3. 
After applying a corona discharging treatment of 10 kVA onto a paper 
substrate having a basis weight of 170 g/m.sup.2 the masterbatch was melt 
extruded onto the paper substrate at 320.degree. C. using a multilayer 
extruding coating die to form polyethylene laminate layers at the layer 
thicknesses shown in Table 2. A glow discharging treatment was applied to 
the surface of the polyethylene layer. 
TABLE 2 
__________________________________________________________________________ 
Construction of Waterproof Resin Layer of Suppor 
Uppermost Layer Interlayer Undermost Layer 
Total TiO.sub.2 
TiO.sub.2 Content 
Thickness 
TiO.sub.2 Content 
Thickness 
TiO.sub.2 Content 
Thickness 
used Amount 
Support 
(wt %) (.mu.) 
(wt %) (.mu.) 
(wt %) (.mu.) 
(g/m.sup.2) 
__________________________________________________________________________ 
A 6 30.mu. 
-- -- -- -- 1.75 
B 10 30 -- -- -- -- 3.0 
C 15 30 -- -- -- -- 4.7 
D 35 30 -- -- -- -- 13.3 
E 10 15 -- -- 0 15 1.5 
F 15 15 -- -- 0 15 2.4 
G 30 15 -- -- 15 15 7.8 
H 35 15 -- -- 0 15 6.7 
I 0 0.5 15 29 10 0.5 4.6 
J 10 2.0 35 15 0 13 6.9 
__________________________________________________________________________ 
(Preparation of Light-Sensitive Material 100) 
A multilayer color photographic printing paper (100) having the layer 
structure show below was prepared by coating various layers on the 
reflective support (A) described above. Each coating liquid was prepared 
as follows. 
Preparation of Coating Liquid for Layer 1: 
In a mixed solvent of 25 g of a solvent (Solv-1), 25 g of a solvent 
(Solv-2), and 180 ml of ethyl acetate were dissolved 153.0 g of a yellow 
coupler (ExY), 15.0 g of a color image stabilizer (Cpd-1), 7.5 g of a 
color image stabilizer (Cpd-2), and 16.0 g of a color image stabilizer 
(Cpd-3) and the solution was dispersed by emulsification in 1,000 g of an 
aqueous 10% gelatin solution containing 60 ml of 10% sodium 
dodecylbenzenesulfonate and 10 g of citric acid to provide an emulsified 
dispersion A. 
On the other hand, a silver chlorobromide emulsion A-1 (cubic, a 3:7 
mixture (by mole ratio of silver) of a large size emulsion having a mean 
grain size of 0.88 .mu.m and a small size emulsion having a mean grain 
size of 0.70 .mu.m, the variation coefficients of the grain size 
distributions of them were 0.08 and 0.10, respectively, in each emulsion, 
0.3 mole % silver bromide was localized at a part of the surfaces of the 
silver chloride grains, and the inside of the silver chloride grain and 
the foregoing local phase of the silver halide grain contained potassium 
hexachloroiridate (IV) in a total amount of 0.1 mg and potassium 
ferrocyanide in a total amount of 1.0 mg) was prepared. In the silver 
chlorobromide, after adding the blue-sensitive sensitizing dyes A and B 
shown below to the large size emulsion and the small size emulsion in the 
amounts of 2.0.times.10.sup.-4 mole and 2.5.times.10.sup.-4 mole, 
respectively per mole of silver, a sulfur sensitizer and a gold sensitizer 
were added to the silver chlorobromide emulsion in the existence of the 
decomposition product of nucleic acid and then the silver chlorobromide 
emulsion was most suitably chemically sensitized. 
The emulsified dispersion A described above was mixed with the silver 
chlorobromide emulsion A-1 and the coating liquid for Layer 1 having the 
composition shown below was prepared. 
The coating liquids for Layer 2 to layer 7 were also prepared by the same 
manner as in preparing the coating liquid for Layer 1. 
As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine 
sodium salt was used. 
Also, Cpd-14 and Cpd-15 were added to each layer in the amounts of 25.0 
mg/m.sup.2 and 50.0 mg/m.sup.2, respectively. 
Furthermore, the size of the silver chlorobromide grains of each silver 
chlorobromide emulsion for following light-sensitive emulsion layers was 
adjusted by the same manner as the case of the silver chlorobromide 
emulsion A-1 and the following spectral sensitizing dyes were used for 
each emulsion layer. 
##STR33## 
(2.0.times.10.sup.-4 mole each to the large size emulsion and 
2.5.times.10.sup.-4 mole each to the small size emulsion per mole of 
silver halide) 
##STR34## 
(4.0.times.10.sup.-4 mole to the large size emulsion and 
5.6.times.10.sup.-4 mole to the small size emulsion per mole of silver 
halide) and 
##STR35## 
(7.0.times.10.sup.-5 mole to the large size emulsion and 
1.0.times.10.sup.-4 mole to the small size emulsion per mole of silver 
halide) 
##STR36## 
(0.9.times.10.sup.-4 mole to the large size emulsion and 
1.1.times.10.sup.-4 mole to the small size emulsion per mole of silver 
halide) 
Furthermore, to the red-sensitive emulsion layer was added the following 
compound in an amount of 2.6.times.10.sup.-3 mole per mole of silver 
halide. 
##STR37## 
Also, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the 
blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the 
red-sensitive emulsion layer in the amounts of 8.5.times.10.sup.-4 mole, 
3.0.times.10.sup.-3 mole, and 2.5.times.10.sup.-4 mol respectively, per 
mole of silver halide. 
Furthermore,4-hydroxy-6-methyl-1,3,3a,7-tetraazindene was added to the 
blue-sensitive emulsion layer and the green-sensitive emulsion layer in 
the amounts of 1.times.10.sup.-4 mole and 2.times.10.sup.-4 mole, 
respectively, per mole of silver halide. 
(Layer Structure) 
The composition of each layer is shown below. The numeral shows the coated 
amount (g/m.sup.2). The case of the silver halide emulsion is shown by the 
silver-converted coated amount. 
Support (A): 
The resin layer at the Layer 1 side contained a bluish dye (ultramarine 
blue). 
______________________________________ 
Layer 1 (Blue-sensitive emulsion layer): 
Silver chlorobromide emulsion A-1 
0.27 
Gelatin 1.22 
Yellow coupler (ExY) 0.79 
Color image stabilizer (Cpd-1) 
0.08 
Color image stabilizer (Cpd-2) 
0.04 
Color image stabilizer (Cpd-3) 
0.08 
Solvent (Solv-1) 0.13 
Solvent (Solv-2) 0.13 
Layer 2 (Color mixing inhibition layer): 
Gelatin 0.90 
Color mixing inhibitor (Cpd-4) 
0.06 
Solvent (Solv-2) 0.25 
Solvent (Solv-3) 0.25 
Solvent (Solv-7) 0.03 
Layer 3 (Green-sensitive emulsion layer): 
Silver chlorobromide emulsion B-1 
0.13 
______________________________________ 
(cubic, a 1:3 mixture (by mole ratio of silver) of a large size emulsion 
having a mean grain size of 0.55 .mu.m and a small size emulsion having a 
mean grain size of 0.39 .mu.m, the variation coefficients of the grain 
size distributions thereof were 0.08 and 0.06, respectively, 0.8 mole % 
silver bromide was localized at a part of the surfaces of the silver 
chloride grains, and the inside of the grains and the local phases of the 
silver bromide contained potassium hexachloroiridate (IV) in the total 
amounts of 0.1 mg and potassium ferrocyanide in the total amounts of 1 mg) 
______________________________________ 
Gelatin 1.45 
Magenta coupler (ExM) 0.16 
Color image stabilizer (Cpd-2) 
0.03 
Color image stabilizer (Cpd-5) 
0.15 
Color image stabilizer (Cpd-6) 
0.01 
Color image stabilizer (Cpd-7) 
0.01 
Color image stabilizer (Cpd-8) 
0.08 
Solvent (Solv-3) 0.50 
Solvent (Solv-4) 0.15 
Solvent (Solv-5) 0.15 
Layer 4 (Color mixing inhibition layer): 
Gelatin 0.70 
Color mixing inhibitor (Cpd-4) 
0.04 
Solvent (Solv-2) 0.18 
Solvent (Solv-3) 0.18 
Solvent (Solv-7) 0.02 
Layer 5 (Red-sensitive emulsion layer): 
Silver chlorobromide emulsion C-1 
0.18 
______________________________________ 
(cubic, a 1:4 mixture (by mole ratio of silver) of a large size emulsion 
having a mean grain size of 0.50 .mu.m and small size emulsion having a 
mean grain size of 0.41 .mu.m, the variation coefficients of the grain 
size distributions thereof were 0.09 and 0.11, respectively, 0.8 mole % 
silver bromide was localized at a part of the surfaces of the silver 
chloride grains, and the insides of the grains and the local phases of 
silver bromide contained potassium hexachloroiridate (IV) in the total 
amounts of 0.3 mg and potassium ferrocyanide in the total amounts of 1.5 
mg.) 
______________________________________ 
Gelatin 0.80 
Cyan coupler (ExC) 0.33 
Ultraviolet absorbent (UV-2) 
0.18 
Color image stabilizer (Cpd-1) 
0.33 
Color image stabilizer (Cpd-2) 
0.03 
Color image stabilizer (Cpd-6) 
0.01 
Color image stabilizer (Cpd-8) 
0.01 
Color image stabilizer (Cpd-9) 
0.01 
Color image stabilizer (Cpd-10) 
0.01 
Color image stabilizer (Cpd-11) 
0.01 
Solvent (Solv-1) 0.01 
Solvent (Solv-6) 0.22 
Layer 6 (Ultraviolet absorption layer): 
Gelatin 0.48 
Ultraviolet absorbent (UV-1) 
0.38 
Color image stabilizer (Cpd-5) 
0.02 
Color image stabilizer (Cpd-12) 
0.15 
Layer 7 (Protective layer) 
Gelatin 1.10 
Acryl-modified copolymer of polyvinyl 
0.05 
alcohol (modified degree 17%) 
Liquid paraffin 0.02 
Color image stabilizer (Cpd-13) 
0.01 
______________________________________ 
Then, the compounds used for preparing the color photographic printing 
paper described above are shown below. 
##STR38## 
By following the same procedure as the case of preparing the sample 100 
except that the support and the addition compound were changed as shown in 
Table 3 below, samples 101 to 169 were prepared. Each addition compound 
was added to Layer 2 (color mixing inhibition layer) and Layer 4 (color 
mixing inhibition layer) such that the total coated amounts became 
4.times.10.sup.-5 mol/m.sup.2. In addition, it was confirmed by the 
cross-sectional photograph that the added compound did not remain in the 
added layer but was diffused almost uniformly in all the layers during 
coating the layer. 
TABLE 3 
______________________________________ 
Used Compound (4 .times. 10.sup.-5 mole/m.sup.2) 
Support 
-- Comp. A Comp. B 
(11) (15) (19) (89) 
______________________________________ 
A 100 110 120 130 140 150 160 
B 101 111 121 131* 141* 151* 161* 
C 102 112 122 132* 142* 152* 162* 
D 103 113 123 133* 143* 153* 163* 
E 104 114 124 134 144 154 164 
F 105 115 125 135* 145* 155* 165* 
G 106 116 126 136* 146* 156* 166* 
H 107 117 127 137* 147* 157* 167* 
I 108 118 128 138* 148* 158* 168* 
J 109 119 129 139* 149* 159* 169* 
______________________________________ 
In the above table, compounds A and B are comparison compounds shown below, 
the compounds (11), (15), (19), and (89) are the compounds of this 
invention, and in sample Nos. 100 to 169, the mark * means the sample of 
this invention. 
##STR39## 
Using each of the samples thus prepared (after finishing the layer 
hardening reaction), the evaluation of the following scratch test was 
performed for determining the extent of pressure fog. 
(Scratch Test Method) 
An acrylic plate applied with a nylon scrubbing brush piece (1 cm.times.3 
cm) was fixed by applying thereto a load of 200 g. Each sample cut into a 
size of 3 cm.times.15 cm was inserted in the acrylic plate (such that the 
light-sensitive layer coated surface was brought into contact with the 
nylon scrubbing brush), and the sample was pulled to the vertical 
direction to the load at a definite speed in the dark to give scratch to 
the surface of the light-sensitive layer with the nylon scrubbing brush. 
The scratch test was carried out in the dark room kept at 25.degree. C. 
and 55% R.H. 
The sample thus scratched was processed using the processing steps shown 
below. About the sample thus obtained, the extent of the yellow fog formed 
by the scratch was visually evaluated. 
The grades of the evaluation were as follows. 
o: Almost no scratch fog was observed. 
.DELTA.: Scratch fog was slightly observed. 
x: Scratch fog was observed. 
xx: Scratch fog was observed on the whole surface and the sample was 
unsuitable for practical use. 
The results Obtained are shown in Table 4 below. 
TABLE 4 
__________________________________________________________________________ 
Addition Compound 
Support 
-- Compound A 
Compound B 
(11) (15) (19) (89) 
__________________________________________________________________________ 
A Sample 100 
Sample 110 
Sample 120 
Sample 130 
Sample 140 
Sample 150 
Sample 160 
.largecircle. 6.8 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
B Sample 101 
Sample 111 
Sample 121 
Sample 131 
Sample 141 
Sample 151 
Sample 161 
.DELTA. 11.5 
.DELTA. 
.DELTA. .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
C Sample 102 
Sample 112 
Sample 122 
Sample 132 
Sample 142 
Sample 152 
Sample 162 
X 13.2 X X .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
D Sample 103 
Sample 113 
Sample 123 
Sample 133 
Sample 143 
Sample 153 
Sample 163 
XX 21.6 
XX XX .DELTA. 
.DELTA. 
.DELTA. 
.DELTA. 
E Sample 104 
Sample 114 
Sample 124 
Sample 134 
Sample 144 
Sample 154 
Sample 164 
.largecircle. 8.5 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
F Sample 105 
Sample 115 
Sample 125 
Sample 135 
Sample 145 
Sample 155 
Sample 165 
.DELTA. 13.1 
.DELTA. 
.DELTA. .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
G Sample 106 
Sample 116 
Sample 126 
Sample 136 
Sample 146 
Sample 156 
Sample 166 
XX 20.2 
XX X .largecircle.-.DELTA. 
.largecircle.-.DELTA. 
.largecircle.-.DELTA. 
.largecircle.-.DELTA. 
H Sample 107 
Sample 117 
Sample 127 
Sample 137 
Sample 147 
Sample 157 
Sample 167 
X 21.5 X X .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
I Sample 108 
Sample 118 
Sample 128 
Sample 138 
Sample 148 
Sample 158 
Sample 168 
X 13.0 X X .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
J Sample 109 
Sample 119 
Sample 129 
Sample 139 
Sample 149 
Sample 159 
Sample 169 
XX 21.0 
X X .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
__________________________________________________________________________ 
The characters of the evaluations were same as the scratch test method 
described before. 
In the above Table 4, the left side shows the scratch evaluation of samples 
100 to 169 and the right side shows the sharpness evaluation C(lines/mm) 
of samples 100 to 109. 
Then, for the purpose of evaluating the effect of the support for the 
sharpness of the photographic light-sensitive material, by contact 
exposing each of the samples 100 to 109 to an optical wedge having 
rectangular patterns of various frequencies using light of the light 
source of an actinometer (manufactured by Fuji Photo Film Co., Ltd.) 
through a vapor deposited interference filter 470 nm, the resolving power 
of yellow color was determined. 
As the character of the resolving power, the frequency C (lines/mm) when a 
CTF value (the ratio of the density difference .DELTA.D.sub.0 between the 
high density portion and the low density portion in the case that the 
frequency was 0, that is, there was no repeat of the rectangular pattern, 
and a continuous light exposure was performed in a very wide area of the 
high light intensity portion and the low light intensity portion and the 
density difference .DELTA.D.sub.c between the high density portion and the 
low density portion in the frequency C (lines/mm) of the rectangular 
pattern: i.e., .DELTA.D.sub.c /.DELTA.D.sub.0) became 0.5 was determined. 
The results obtained are shown in Table 4 above. The larger value of C 
means that the resolving power is higher. If the value of C is about 10 or 
more, the light-sensitive material is said to have a high resolving power. 
______________________________________ 
Tank 
Processing 
Temperature 
Time Replenisher* 
volume 
step (.degree.C.) 
(sec.) (ml) (liter) 
______________________________________ 
Color 35 45 161 10 
development 
Blix 30-35 45 215 10 
Rinse (1) 30-35 20 -- 5 
Rinse (2) 30-35 20 -- 5 
Rinse (3) 30-35 20 350 5 
Drying 70-80 60 
______________________________________ 
*: The replenishing amount was per 1 m.sup.2 of each sample. 
[Rinse was carried out by a 3 tank counter current system of (1) to (3). 
The composition of each processing liquid was as follows. 
______________________________________ 
Replenisher 
Color Developer Tank liquid 
______________________________________ 
Water 800 ml 800 ml 
Ethylenediamine-N,N,N',N'- 
1.5 g 2.0 g 
tetramethylenephosphonic acid 
Potassium bromide 0.015 g -- 
Triethanolamine 8.0 g 12.0 g 
Sodium chloride 1.4 g -- 
Potassium carbonate 25 g 25.0 g 
N-Ethyl-N-(.beta.-methanesulfonamido- 
5.0 g 7.0 g 
ethyl)-3-methyl-4-aminoaniline 
sulfate 
N,N-Bis(carboxymethyl)hydrazine 
4.0 g 5.0 g 
N,N-Di(sulfoethyl)hydroxyl- 
4.0 g 5.0 g 
amine.1Na 
Fluorescent brightening agent 
1.0 g 2.0 g 
(WHITEX 4B, trade name, made by 
Sumitomo Chemical Company, Ltd.) 
Water to make 1000 ml 1000 ml 
pH (25.degree. C.) 10.05 10.45 
______________________________________ 
Blix Liquid (Tank liquid = replenisher) 
Water 400 ml 
Ammonium thiosulfate (700 g/liter) 
100 ml 
Sodium sulfite 17 g 
Ethylenediaminetetraacetic acid iron(III) 
55 g 
ammonium 
Disodium ethylenediaminetetraacetate 
5 g 
Ammonium bromide 40 g 
Water to make 1000 ml 
pH (25.degree. C.) 6.0 
Rinse liquid (Tank liquid = replenisher) 
Ion exchanged water (content of each of Ca 
and Mg was less than 3 ppm). 
______________________________________ 
From the results obtained, the following matters were confirmed. 
In the samples 100, 110, and 120 and the samples 104, 114, and 124 using 
the support A and the support B each having the waterproof resin coated 
layers having a content of titanium oxide of less than 2.0 g/m.sup.2, the 
problem of the scratch fog does not occur without using the compound of 
the present invention but the sharpness is low. By using the support 
having the waterproof resin coated layers having a titanium oxide content 
of 2.0 g/m.sup.2 or more and without using the compound of the present 
invention, the sharpness can be improved but the formation of the scratch 
fog is increased (samples 102, 112, 122, etc.). It can be seen that the 
extent of the scratch fog is increased with the increase of the amount 
titanium oxide used (samples 103, 113, 123, etc.). On the other hand, it 
can be seen that by using the compound of the present invention, the 
photographic light-sensitive material which causes less scratch fog and is 
excellent in sharpness can be obtained (samples 131, 141, 151, 161, etc.). 
EXAMPLE 3 
(Preparation of Support) 
A mixed composition of a polyester having 6.5 of limited viscosity, 
synthesized by the condensation polymerization of a dicarboxylic acid 
composition and ethylene glycol, and titanium oxide (A-10, trade name, 
made by Titan Kogyo K.K.) as shown in Table 5 below was melt-mixed by a 
biaxial mixing extruding machine at 300.degree. C. and melt-extruded onto 
the surface of a base paper of 180 .mu.m in thickness from a T die to form 
a laminate layer having a thickness of 30 .mu.m. Then, a resin composition 
containing calcium carbonate was melt-extrude onto the opposite surface of 
the base paper at 300.degree. C. to form a laminate layer having a 
thickness of 30 .mu.m. After applying a corona discharging treatment onto 
the resin surface of the reflective support having the laminated layers at 
the side of being coated with silver halide emulsion layers, the subbing 
coating liquid having the composition shown below was coated thereon at 5 
ml/m.sup.2 and dried for 2 minutes at 80.degree. C. to provide 
photographic supports K to R. 
______________________________________ 
(Subbing Composition) 
______________________________________ 
Compound (EXU1) 0.2 g 
Compound (EXU2) 0.001 g 
Water 35 ml 
Methanol 65 ml 
Gelatin 2 g 
pH 9.5 
______________________________________ 
TABLE 5 
______________________________________ 
Coated resin (molar 
ratio of dicarboxylic acid 
Support 
composition of polyester) 
TiO.sub.2 (g/m.sup.2) 
______________________________________ 
K Polyester (Terephthalic acid 100) 
1.8 
L " 2.5 
M " 4.5 
N " 9.5 
O " 15.0 
P " 22.0 
Q Polyester (Terephthalic acid/ 
1.8 
isophthalic acid 80/20) 
R Polyester (Terephthalic acid/ 
9.5 
isophthalic acid 80/20) 
EXU1 
##STR40## 
EXU2 
C.sub.12 H.sub.25 O(CH.sub.2 CH.sub.2 O).sub.10 H 
Comparison Compound C 
##STR41## 
______________________________________ 
(Preparation and Evaluation of Light-Sensitive Material) 
A light-sensitive material 200 was prepared by forming the layers same as 
these of the light-sensitive material 100 in Example 2 on the reflective 
support K described above. 
Also, by following the same procedure as the sample 200 except that the 
support and the addition compound were changed as shown in Table 6, 
samples 201 to 263 were prepared. The addition compound was added to Layer 
2 and Layer 4 (color mixing inhibition layers) such that the total coated 
amounts became 4.times.10.sup.-5 mole/m.sup.2. In addition, it was 
confirmed by the cross-sectional photograph that the addition compound did 
not remain in the added layer but was almost uniformly diffused in the 
whole layers during coating. 
TABLE 6 
______________________________________ 
Used Compound (4 .times. 10.sup.-5 mole/m.sup.2) 
(The compound was added to the 2nd and 4th layers, 
individually. The comound diffuses into the whole 
coating layer.) 
Spt -- Comp. A Comp. C 
(3) (38) (42) (57) (81) 
______________________________________ 
K 200 208 216 224 232 240 248 256 
L 201 209 217 225* 233* 241* 249* 257* 
M 202 210 218 226* 234* 242* 250* 258* 
N 203 211 219 227* 235* 243* 251* 259* 
O 204 212 220 228* 236* 244* 252* 260* 
P 205 213 221 229* 237* 245* 253* 261* 
Q 206 214 222 230 238 246 254 262 
R 207 215 223 231* 239* 247* 255* 263* 
______________________________________ 
In the above table, compound C was a comparison compound, the compounds 
(3), (38), (42), (57), and (81) were compounds of this invention, and in 
the samples 200 to 263, the mark * means the sample of this invention. 
On the samples obtained, the same evaluations as in Example 2 were 
performed. Also, for the purpose of evaluating the effect of the support 
for the sharpness of the sample, the CTF evaluation as in Example 2 was 
carried out on the samples 201 to 207. 
The results obtained are shown in Table 7 below. 
TABLE 7 
__________________________________________________________________________ 
Addition Compound 
Sup. 
-- Compound A 
Compound C 
(3) (38) (42) (57) (81) 
__________________________________________________________________________ 
K Sample 200 
Sample 208 
Sample 216 
Sample 224 
Sample 232 
Sample 240 
Sample 248 
Sample 256 
.largecircle. 5.8 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
L Sample 201 
Sample 209 
Sample 217 
225 Sample 233 
Sample 241 
Sample 249 
Sample 257 
.DELTA. 7.1 
.DELTA. 
.DELTA. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
M Sample 202 
Sample 210 
218 X Sample 226 
Sample 234 
Sample 242 
Sample 250 
Sample 258 
X 10.9 
X X .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
N Sample 203 
Sample 211 
Sample 219 
Sample 227 
Sample 235 
Sample 243 
Sample 251 
Sample 259 
X-XX 18.3 
X X-XX .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
O Sample 204 
Sample 212 
Sample 220 
Sample 228 
Sample 236 
Sample 244 
Sample 252 
Sample 260 
XX 20.2 
X XX .largecircle.-.DELTA. 
.largecircle.-.DELTA. 
.largecircle.-.DELTA. 
.largecircle.-.DELTA. 
.largecircle.-.DELTA. 
P Sample 205 
Sample 213 
Sample 221 
Sample 229 
Sample 237 
Sample 245 
Sample 253 
Sample 261 
XX 24.6 
XX XX .DELTA. 
.DELTA. 
.DELTA. 
.DELTA. 
.DELTA. 
Q Sample 206 
Sample 214 
Sample 222 
Sample 230 
Sample 238 
Sample 246 
Sample 254 
Sample 262 
.largecircle. 5.6 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
R Sample 207 
Sample 215 
Sample 223 
Sample 231 
Sample 239 
Sample 247 
Sample 255 
Sample 263 
X-XX 18.1 
X X-XX .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
__________________________________________________________________________ 
The characters of the evaluations were same as the scratch test method 
described before. In the above Table, the left side shows the scratch 
evaluation of samples 200 to 263 and the right side shows the sharpness 
evaluation c(lines/mm) of samples 200 to 207. 
In the samples 216 to 223 using the comparison compound C, coloring with 
the compound C after processing was very severe. 
From the results obtained, it can be seen that by using the support having 
the waterproof resin coated layer having the titanium oxide content of at 
least 2.0 g/m.sup.2, the sharpness is excellent but the scratch for is 
increased. It can be also seen that the extent of the formation of the 
scratch fog is increased with the increase of the amount of titanium oxide 
used. On the other hand, it can be seen that by using the compound of this 
invention, the light-sensitive material giving less scratch fog and being 
excellent in sharpness can be obtained. 
EXAMPLE 4 
By following the same procedures as the case of preparing the samples 100 
to 169 in Example 2 and the samples 200 to 263 in Example 3 except that 
the compositions of Layers 2, 3, and 4 were changed as shown below and the 
dye shown below was used as the irradiation inhibiting dye (since the 
compound of this invention has the absorption in the same visible region 
as the dye, the actual irradiation inhibition effect of the 
light-sensitive material was the sum of the effect of the irradiation 
inhibition dye and the effect of the compound of this invention), samples 
100' to 169' and samples 200' to 263' were prepared. 
______________________________________ 
Layer 2 (Color mixing inhibition layer) 
Gelatin 0.99 
Color mixing inhibitor (Cpd-A) 
0.04 
Color mixing inhibitor (Cpd-B) 
0.04 
Solvent (Solv-2) 0.16 
Solvent (Solv-3) 0.08 
Layer 3 (Green-sensitive emulsion layer) 
Silver chlorobromide emulsion B-1 
0.13 
Gelatin 1.24 
Magenta coupler (M-A) 0.26 
Color image stabilizer (Cpd-8) 
0.03 
Color image stabilizer (Cpd-5) 
0.04 
Color image stabilizer (Cpd-6) 
0.02 
Color image stabilizer (Cpd-2) 
0.02 
Solvent (Solv-8) 0.30 
Solvent (Solv-9) 0.15 
Layer 4 (Color mixing inhibition layer) 
Gelatin 0.70 
Color mixing inhibitor (Cpd-A) 
0.03 
Color mixing inhibitor (Cpd-B) 
0.03 
Solvent (Solv-2) 0.11 
Solvent (Solv-3) 0.06 
Solvent (Solv-10) 0.02 
______________________________________ 
The compounds newly used in the above sample are shown below. 
##STR42## 
On the samples obtained, the same evaluations as in Example 2 were 
performed. The results obtained were almost same as those in Example 2 and 
the effect was remarkable in the construction of the present invention. 
EXAMPLE 5 
A color negative film (a) wherein the support was a triacetyl cellulose and 
a color negative film (b) wherein the support was composed of polyethylene 
terephthalate and polyethylene naphthalate were used. The frames of the 
same scene photographed to these color negative films each was printed to 
the samples prepared in Examples 2 and 3 using an automatic printer and 
the psychological evaluation of the sharpness of this invention was 
performed. The results obtained showed that the light-sensitive material 
having the larger value of the evaluation C (lines/mm) for sharpness 
showed a more excellent sharpness. Furthermore, when the color negative 
film (b) wherein the support was composed of polyethylene terephthalate 
and polyethylene naphthalate was used, the sharpness of the 
light-sensitive material was very excellent. 
EXAMPLE 6 
On the samples prepared in Examples 2 and 3, the same evaluations as in 
Example 2 were carried out except that the following light exposure was 
performed and the results obtained were almost same as these in Examples 2 
and 3. 
(Light Exposure) 
As the light source, light of 473 nm obtained by converting the wavelength 
of the YAG solid state laser (oscillation wavelength, 946 nm) using a 
semiconductor laser GaAlAs (oscillation wavelength 808.5 nm) as an 
excitation light source by the SHG crystal of KNbO.sub.3, light of 532 nm 
obtained by converting the wavelength of a YVO.sub.4 solid state laser 
(oscillation wavelength, 1064 nm) using a semiconductor laser GaAlAs 
(oscillation wavelength, 808.7 nm) as an excitation light source by the 
SHG crystal of KTP, and AlGaInP (oscillation wavelength, about 670 nm, 
Type TPLD9211, made by TOSHIBA CORPORATION) were used. In the scanning 
apparatus being used, the laser light could successively scan the color 
photographic printing paper moving to the vertical direction to the 
scanning direction by a rotary polyhydron. By using the scanning 
apparatus, the relation D-logE of the density (D) of the light-sensitive 
material and the light intensity (E) was obtained by changing the light 
intensity. In this case, the light intensity of each of the three lights 
of three wavelengths was modulated using an external modulator of control 
the exposure intensity. The scanning exposure was carried out at 400 dpi 
and in this case, the average exposure time per pixel was about 
5.times.10.sup.-8 second. The temperature of the semiconductor laser was 
kept at a constant value using a Peltier element for restraining the 
fluctuation of the light intensity. 
By incorporating the compound of this invention in the layers constituting 
the photographic light-sensitive material, the formation of the pressure 
fog can be effectively restrained even by using a reflective support 
giving a high sharpness. 
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 spirits and scope thereof.