Method of preserving colored images

A method of preserving colored images formed by exposing imagewise a heat developable color photosensitive element which has a construction which includes, on a support, at least a photosensitive silver halide, a binder and a dye providing substance which forms or releases a diffusible dye in proportion, or in inverse proportion, to a reaction in which the silver halide is reduced to silver; thereafter or simultaneously heating said element to form a diffusible dye; and transferring the diffusible dye image to a dye fixing element, wherein the photosensitive element or the dye fixing element further comprises at least one of a compound of which the quenching rate constant for the excited triplet of arylazonaphthol yes is at least 1.times.10.sup.5 M.sup.-1 .multidot.sec.sup.-1 and a compound of which the quenching rate constant for singlet state oxygen is at least 1.times.10.sup.7 M.sup.-1 .multidot.sec.sup.-1.

FIELD OF THE INVENTION 
This invention concerns a method of preserving colored images formed by 
heat development. 
BACKGROUND OF THE INVENTION 
Photographic methods in which silver halides are used have been widely used 
in the past since they provide better photographic characteristics, such 
as photographic speed and gradation control, than do other photographic 
methods such as electrophotography or diazo photography. Color diffusion 
transfer processes in which a photosensitive element which has a silver 
halide emulsion layer and an image receiving element which has an image 
receiving layer are superimposed on one another and an alkaline processing 
composition is spread in the form of a layer inside the combination, or 
the combination is immersed in an alkali processing bath, are included 
among photographic methods in which silver halides are used. In recent 
years, techniques from which images can be obtained easily and quickly by 
the application of a dry process with heating, for example, have been 
developed apart from the wet methods using conventional development baths 
for the formation of an image with photosensitive materials in which 
silver halides are used. 
Methods of image formation with thermal development have been disclosed, 
for example, in JP-A-57-179840, JP-A-57-186774, JP-A-57-198458, 
JP-A-57-207250, JP-A-58-58543, JP-A-58-79247, JP-A-58-116537, 
JP-A-58-149046, JP-A-59-48764, JP-A-59-65839, JP-A-59-71046, 
JP-A-59-87450, JP-A-59-88730, JP-A-62-253159 and European Patent 
220,746A2. (The term "JP-A" as used herein means an "unexamined published 
Japanese patent application".) 
These are methods in which mobile dyes are formed or released in 
proportion, or in inverse proportion, to the reaction when a 
photosensitive silver halide and/or organic silver salt is reduced by heat 
development to silver, and the mobile dye is transferred to a dye fixing 
element. 
The method of forming images by transferring a diffusible dye formed by 
heat development to an image fixing element has a major advantage in that 
the dye image can be obtained easily and quickly. However, when the image 
obtained is stored for a prolonged period of time, the colors are liable 
to fade or change for reasons different from those seen in color images 
formed by the ordinary wet processing. This is because heat is applied 
during the image formation or transfer and, therefore, the dyes cause 
denaturation by themselves, or substances which impart adverse influences 
with respect to color fading or change are formed and transferred to the 
dye fixing element together with the dyes. 
SUMMARY OF THE INVENTION 
Hence, an object of this invention is to provide a method of preserving 
colored images produced by transferring a diffusible dye formed by heat 
development to a dye fixing element, with improved storage properties over 
prolonged periods of time. 
The present invention has been made based on the finding that in order to 
improve the storage properties of color images produced by transferring a 
diffusible dye formed by heat development to a dye fixing element, a 
compound having specified physical properties is effective. 
This object of the invention has been realized by providing a method of 
preserving colored images formed by exposing imagewise a heat developable 
color photosensitive element which has a construction which includes, on a 
support, at least a photosensitive silver halide, a binder and a dye 
providing substance which forms or releases a diffusible dye in 
proportion, or in inverse proportion, to a reaction in which the silver 
halide is reduced to silver; thereafter or simultaneously heating said 
element to form a diffusible dye; and transferring the diffusible dye 
image to a dye fixing element, wherein the photosensitive element or the 
dye fixing element further comprises at least one of a compound of which 
the quenching rate constant for the excited triplet of arylazonaphthol 
dyes is at least 1.times.10.sup.5 M.sup.-1 .multidot.sec.sup.-1 and/or a 
compound of which the quenching rate constant for singlet state oxygen is 
at least 1.times.10.sup.7 M.sup.-1 .multidot.sec.sup.-1. 
It has been found that in order to improve the storage properties of color 
images produced by transferring a diffusible dye formed by heat 
development to a dye fixing element, the use of at least one of a compound 
of which the quenching rate constant (referred to below as k.sub.q 
.multidot.T.sub.1) for the excited triplet of arylazonaphthol dyes 
(T.sub.1) is at least 1.times.10.sup.5 M.sup.-1 .multidot.sec.sup.-1, and 
preferably at least 5.times.10.sup.5 M.sup.-1 .multidot.sec.sup.-1, and/or 
a compound of which the quenching rate constant for singlet oxygen is at 
least 1.times.10.sup.7 M.sup.-1 .multidot.sec.sup.-1, and preferably at 
least 1.times.10.sup.8 M.sup.-1 .multidot.sec.sup.-1, is very effective 
for this purpose. 
The object of this invention can be realized by including these compounds 
in the colored image, and the compounds of the invention may be previously 
added to the dye fixing element. Further, they may be tansferred from the 
heat developable color photosensitive element to the dye fixing element 
together with the dye. In either case, the compounds of the invention may 
be present in any of the layers on the side on which the colored image is 
finally included on a support. The best effect is achieved when the 
compounds are added to the dye fixing layer of the dye fixing element or 
to a layer adjacent thereto. 
The amount of the compound of this invention used differs according to the 
type of compound, but the compounds are preferably used in a mol to mol 
ratio with respect to the dye providing compound within the range from 
0.01 to 1, and more preferably within the range from 0.1 to 5. 
In the present invention, the arylazonaphthol dye means a dye having the 
following structure:

DETAILED DESCRIPTION OF THE INVENTION 
The compounds of the invention are described in detail below. 
In this invention, the compounds of which the quenching rate constant 
(k.sub.q .multidot.T.sub.1) for triplet arylazonaphthol dyes in at least 
1.times.10.sup.5 M.sup.-1 .multidot.sec.sup.-1 can be determined using a 
test method such as that described below. 
First, a method in which a sample solution contained in a quartz cell is 
flashed using a pulse laser or a flash tube as the exciting light source 
is generally used for generating photo-excited triplet states. The 
ultraviolet and visible absorption spectra of molecules which have been 
excited in this way are monitored using a photomultiplier tube to observe 
the decay in the absorption at the wavelength of the absorption of the 
triplet state of the dye using a xenon lamp as a monitoring light source. 
The decay curve is represented as a single log plot and the life of the 
excited triplet can be obtained from the absolute value of the slope of 
the linear plot. 
Flash photolysis apparatus with a flash lamp (FXQ33-2) made by the EG and G 
Company as the exciting light source and a 150 W xenon lamp for the 
monitoring light was used in these tests. 
The arylazonaphthol dye is dissolved to provide a 20 .mu.M solution in a 
mixed solvent consisting of tetrahydrofuran and water (this may be varied 
within the range from 1/1 to 3/1 by volume) and the life (.tau..sub.0) of 
the excited triplet with the dye alone is obtained without a degassing 
treatment. Next, the compound which is to be tested is added in varying 
concentrations; the life (.tau.i, .tau.j, . . . ) of the triplet is 
obtained in the same way as before, a Stern-Volmer plot is made and the 
gradient of this plot is obtained. The gradient is equivalent to k.sub.q 
.multidot.T.sub.1 .multidot..tau..sub.0 and so the quenching rate constant 
(K.sub.q .multidot.T.sub.1, units M.sup.-1 .multidot.sec.sup.-1) can be 
obtained by dividing by .tau..sub.0. 
This method for measuring quenching rate constants of excited triplet is 
based on the methods described in the literature, for example by G. Porter 
and M. W. Windsor in J. Chem. Phys., 1953, 2088 (1954), by N. Yamamoto, Y. 
Nakao and H. Tsubomura in Bull. Chem. Soc. Jpn., 39, 2603 (1966) and by 
Kira and Nishi in Rikagaku Kenkyujo Hokoku, 44, 56 (1968). 
Alternatively, compounds of which the quenching rate constant (K.sub.q 
.multidot.O.sub.2) for singlet oxygen is at least 1.times.10.sup.7 
M.sup.-1 .multidot.sec.sup.-1 can be determined using the following test 
method. 
A method in which a rubrene (a representative structure of which appears 
below) .alpha. autosensitizing singlet oxidation reaction is used has 
already been reported for measuring quenching rate constants (K.sub.q 
.multidot.O.sub.2) for singlet oxygen (.sup.1 O.sub.2). 
##STR2## 
If rubrene is represented by R and oxygen is represented by O.sub.2, this 
method can be represented by the following equations. 
##EQU1## 
If a steady state is assumed for [.sup.1 O.sub.2 *], then: 
##EQU2## 
Hence, 
##EQU3## 
When t=0, [R]=[R.sub.0 ] and so: 
##EQU4## 
Therefore: 
##EQU5## 
In the absence of a compound being tested, [Q]=0: 
##EQU6## 
The same concentration of rubrene is used in systems which do and do not 
contain a compound for testing and the same amount of light is directed 
onto the same volume of solution. 
EQU T.sub.it =R.sub.i't 
EQU [R].sub.0.sup.Q =[R].sub.0.sup.0 =[R] 
##EQU7## 
In chloroform solution: 
EQU K.sub.OX =5.3.times.10.sup.7, kd=1.7.times.10.sup.4 
Hence, in the tests, [R] is set equal to 5.times.10.sup.-4 M, and Q is set 
equal to 10.sup.-3 M and the samples are irradiated with visible light 
only using a sharp cut filter SC-42, made by the Fuji Photo Film Co., Ltd. 
This method of measuring the quenching rate constant for singlet oxygen is 
based on methods described by D. J. Carlsson et at., Can. J. Chem., 52, 
3728 (1974), B. M. Monroe et al., J. Phys. Chem., 83, 591 (1979), and B. 
M. Monroe, J. Phys. Chem., 81, 1861 (1977). 
Compounds suitable for use are selected from among those compounds which 
can be represented by the general formuale [I] to [V] indicated below. 
##STR3## 
In this formula, R.sup.1 represents a hydrogen atom, alkyl group, acyl 
group, sulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl 
group or trialkylsilyl group, and A represents a group of non-metal atoms 
which, together with 
##STR4## 
complete a five or six membered ring. R.sup.2, R.sup.3 and R.sup.4 each 
represents a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, 
aryl group, aryloxy group, aralkyl group, aralkoxy group, alkenyl group, 
alkenoxy group, acylamino group, halogen atom, alkylthio group, 
diacylamino group, arylthio group, alkoxycarbonyl group, acyloxy group, 
acyl group or sulfonamido group, and they may be the same or different. 
Moreover, five or six membered bis-spiro compounds containing A are 
included among the compounds represented by the general formula [I]. 
##STR5## 
In this formula, R.sup.1 is the same as the R.sup.1 group defined in 
connection with general formula [I]. R.sup.5 represents an alkyl group, 
alkoxy group, alkoxycarbonyl group, arylthio group, arylsulfinyl group, 
arylsulfonyl group, aralkyl group, halogen atom, aryl group or acyl group, 
and R.sup.6 represents a hydrogen atom, alkyl group, alkoxy group (but 
R.sup.1 O-- and R.sup.6 are not the same), aralkyloxy group (but R.sup.1 
O-- and R.sup.6 are not the same), alkylthio group, aralkylthio group, 
acylamino group, acyl group, alkylamino group, arylamino group or 
heterocyclic amino group. R.sup.7 represents a hydrogen atom, halogen 
atom, alkyl group, arylthio group, alkylthio group, arylsulfonyl group, 
arylsulfinyl group, aralkyl group, aryl group, aryldithio group or an 
aryloxy group. 
##STR6## 
In this formula, R.sup.8 represents a hydrogen atom or linear or branched 
chain alkyl group or alkenyl group; R.sup.9 represents a linear or 
branched chain alkyl group or alkenyl group, and R.sup.8 and R.sup.9 may 
be the same or different. Furthermore, R.sup.1 has the same meaning as 
R.sup.1 in general formula [I]. Furthermore, substituents R.sup.8 and 
R.sup.9 may contain an --NHCO-- bond within the group. 
##STR7## 
In this formula, R.sup.10 represents an alkyl group, alkenyl group, aryl 
group, aralkyl group, heterocyclic group or group which can be represented 
by R.sup.18 CO, R.sup.19 SO.sub.2 or R.sup.20 NHCO. Here, R.sup.18, 
R.sup.19 and R.sup.20 each independently represents an alkyl group, 
alkenyl group, aryl group or heterocyclic group. R.sup.11 and R.sup.12 
each independently represents a hydrogen atom, halogen atom, alkyl group, 
alkenyl group, alkoxy group or alkenoxy group, and R.sup.13, R.sup.14, 
R.sup.15, R.sup.16 and R.sup.17 each independently represents a hydrogen 
atom, alkyl group, alkenyl group or aryl group. 
##STR8## 
In this formula, B represents a group of non-metal atoms which, together 
with the adjacent atoms forms a five to seven membered ring. R.sup.30 
represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, 
acyl group, sulfonyl group, sulfinyl group, oxy radical group or hydroxyl 
group, and R.sup.31, R.sup.32, R.sup.33 and R.sup.34 may be the same or 
different, each representing a hydrogen atom or alkyl group. 
The anti-color fading agents represented by the general formulae [I] to [V] 
are now described in detail below. 
##STR9## 
Here, R.sup.1 represents a hydrogen atom; an alkyl group which preferably 
has from 1 to 22 carbon atoms (for example, methyl, ethyl, propyl, 
n-octyl, dodecyl, hexadecyl); an acyl group (for example, acetyl, benzoyl, 
pentanoyl, (2,4-di-tert-amylphenoxy)acetyl); a sulfonyl group (for 
example, methanesulfonyl, butanesulfonyl, benzenesulfonyl, 
toluenesulfonyl, hexadecanesulfonyl); a carbamoyl group (for example, 
N-methylcarbamoyl, N,N-diethylcarbamoyl, N-dodecylcarbamoyl, 
N-phenylcarbamoyl); a sulfamoyl group (for example, N-methylsulfamoyl, 
N,N-dimethylsulfamoyl, N-tetradecylsulfamoyl, N-phenylsulfamoyl); an 
alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, 
benzyloxycarbonyl, phenoxycarbonyl); or a trialkylsilyl group (for 
example, trimethylsilyl, dimethylbutylsilyl); and A represents a group of 
non-metal atoms which, together with 
##STR10## 
forms a five or six membered ring. This ring may be substituted, and the 
preferred substituent groups include alkyl groups (for example, methyl, 
t-butyl, cyclohexyl, octyl, dodecyl, octadecyl); alkoxy groups (for 
example, methoxy, butoxy, dodecyloxy); aryl groups (for example, phenyl); 
aryloxy groups (for example, phenoxy); aralkyl groups (for example, 
benzyl, phenethyl); aralkoxy groups (for example benzyloxy, phenethyloxy); 
alkenyl groups (for example, allyl); N-substituted amino groups (for 
example, alkylamino, dialkylamino, N-alkyl-N-arylamino, piperadino) and 
heterocyclic groups (for example, benzothiazolyl, benzooxazoyl). The 
above-mentioned alkyl groups and aryl groups may be further substituted, 
preferably with one or more halogen atoms, hydroxyl groups, carboxyl 
groups, alkoxycarbonyl groups, acyloxy groups, sulfo groups, sulfonyloxy 
groups, amido groups (for example, acetamido, ethanesulfonamido, 
benzamido), alkoxy groups and aryloxy groups. 
R.sup.2, R.sup.3 and R.sup.4 each independently represents a hydrogen atom, 
alkyl group (for example, methyl, t-butyl, cyclopentyl, n-octyl, t-octyl, 
dodecyl, octadecyl); cycloalkyl group (for example, cyclohexyl); alkoxy 
group (for example, methoxy, butoxy, dodecyloxy); aryl group (for example, 
phenyl); aryloxy group (for example phenoxy); aralkyl group (for example, 
benzyl, phenethyl), aralkoxy group (for example, benzyloxy, phenethyloxy); 
alkenyl group (for example, allyl); alkenoxy group (for example, 
allyloxy); acylamino group (for example, acetylamino, benzamido, 
(2,4-di-tert-amylphenoxy)acetylamino); halogen atom (for example, 
chlorine, bromine); alkylthio group (for example, ethylthio, dodecylthio, 
octadecylthio); diacylamino group (for example, succinimido, hydantoinyl); 
arylthio group (for example, phenylthio); alkoxycarbonyl group (for 
example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl); acyloxy 
group (for example, acetyloxy, benzoyloxy); acyl group (for example, 
methylcarbonyl); or a sulfonamido group. 
Moreover, five and six membered bis-spiro compounds which contain A are 
included among the compounds represented by general formula [I]. The 
bis-spiro compounds which are useful in the invention can be represented 
by the general formula [I'] indicated below. 
##STR11## 
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.1', R.sup.2', R.sup.3' and 
R.sup.4' have the same significance as R.sup.1, R.sup.2, R.sup.3 and 
R.sup.4 in general formula [I]. 
Those compounds in which the total number of carbon atoms included in 
R.sup.2, R.sup.3, R.sup.2 and A in the aforementioned general formula [I] 
is at least 8, and those compounds represented by general formula [I'] 
have low diffusibility and are suitable for being selectively located in a 
specified hydrophilic layer of a dye fixing material. Furthermore, 
5-hydroxycoumarans and 6-hydroxychromans in which one of R.sup.2 and 
R.sup.3 in the aforementioned general formula [I] is a hydrogen atom, and 
6,6'-dihydroxybis-2,2'-spirochromans, in which the total number of carbon 
atoms included in the molecule is preferably up to about 40 are especially 
useful for purposes of the present invention. Most desirably, R.sup.2, 
R.sup.3, R.sup.4, R.sup.2', R.sup.3' and R.sup.4' in general formula [I] 
and general formula [I'] are alkyl groups, alkoxy groups, aryl groups, 
aryloxy groups or arylthio groups. 
##STR12## 
In this formula, R.sup.1 is the same as R.sup.1 defined in general formula 
[I]; R.sup.5 is preferably a substituted or branched chain alkyl group 
which has from 1 to 22 carbon atoms (for example, methyl, t-butyl, 
n-octyl, t-octyl, dodecyl, hexadecyl); an alkoxy group which has from 1 to 
22 carbon atoms (for example, methoxy, ethoxy, octyloxy, tetradecyloxy); 
an alkoxycarbonyl group (for example, ethoxycarbonyl); an arylthio group 
(for example, phenylthio); an arylsulfinyl group (for example, 
phenylsulfinyl); an arylsulfonyl group (for example, phenylsulfonyl); an 
aralkyl group (for example, benzyl, phenethyl); a halogen atom (for 
example, chlorine, bromine); an aryl group (for example, phenyl, .alpha.- 
or .beta.-naphthyl); or an acyl group (for example, acetyl, butanoyl, 
benzoyl). R.sup.6 preferably represents a hydrogen atom; an alkyl group 
which has from 1 to 22 carbon atoms (for example, methyl, ethyl, t-butyl, 
t-octyl, n-dodecyl, n-hexadecyl); an alkoxy group which has from 1 to 22 
carbon atoms (for example, methoxy, n-butyloxy, n-octyloxy, n-dodecyloxy, 
n-tetradecyloxy, 2-ethylhexyloxy; but R.sup.1 O-- and R.sup.6 are not the 
same substituent group); an aralkyloxy group which has from 7 to 22 carbon 
atoms (for example, benzyloxy .beta.-phenethyloxy; but R.sup.1 O-- and 
R.sup.6 are not the same substituent group); an alkylthio group which has 
from 1 to 22 carbon atoms (for example, methylthio, octylthio, 
dodecylthio, hexadecylthio); an aralkylthio group (for example, 
benzylthio, .beta.-phenethylthio); an acylamino group which has from 2 to 
22 carbon atoms (for example, acetylamino, benzamido); an acyl group which 
has from 2 to 22 carbon atoms (for example acetyl, butanoyl, benzoyl); an 
alkylamino group which has from 1 to 22 carbon atoms (for example, 
methylamino, ethylamino, N,N-dimethylamino, N-methyl-N-dodecylamino); an 
arylamino group which has from 6 to 22 carbon atoms (for example, 
phenylamino, N-phenyl-N-methylamino, .beta.-naphthylamino); or a 
heterocyclic amino group (for example, a group which can be represented by 
the formulae indicated below): 
##STR13## 
R.sup.7 preferably represents a hydrogen atom; a halogen atom (for 
example, chlorine, bromine); an alkyl group which has from 1 to 22 carbon 
atoms (for example, methyl, ethyl, t-butyl, t-octyl, t-amyl, t-hexyl, 
n-hexadecyl); an arylthio group which has from 6 to 22 carbon atoms (for 
example, phenylthio); an alkylthio group which has from 1 to 22 carbon 
atoms (for example, methylthio, octylthio, dodecylthio, octadecylthio); an 
arylsulfonyl group which has 6 to 22 carbon atoms (for example, 
phenylsulfonyl); an arylsulfinyl group which has from 6 to 22 carbon atoms 
(for example, phenylsulfinyl); an aralkyl group which has from 7 to 32 
carbon atoms (for example, benzyl, .alpha.- or .beta.-phenethyl); an aryl 
group which has from 6 to 32 carbon atoms (for example, phenyl, .alpha.- 
or .beta.-naphthyl); an aryldithio group which has from 6 to 32 carbon 
atoms; or an aryloxy group which has from 6 to 22 carbon atoms. 
Furthermore, the groups R.sup.5, R.sup.6 and R.sup.7 described above may 
be optionally substituted with further R.sup.5, R.sup.6 and R.sup.7 groups 
or hydroxyl groups. 
Among the compounds represented by general formula [II], the hindered 
phenol compounds represented by the general formula [II'] are preferred. 
Further, the compounds represented by the general formula [II'] are the 
most preferred among those represented by the general formulae [I] to [V]. 
##STR14## 
Here, B' represents --S--, --S--S--, --O--, --CH.sub.2 --S--CH.sub.2 --, 
--SO.sub.2 --, --SO--, --CH.sub.2 --O--CH.sub.2 --, 
##STR15## 
R.sup.21, R.sup.22, R.sup.23 and R.sup.24 each preferably and independently 
represents a hydrogen atom; an alkyl group which has from 1 to 20 carbon 
atoms; an aryl group; an aralkyl group; an alkylthio group; a halogen 
atom; an alkoxy group; an arylthio group; an aralkoxy group; an aryloxy 
group; --COOR.sup.29 ; --NHCOR.sup.29 ; --NHSO.sub.2 R.sup.29 ; --SO.sub.2 
R.sup.29 ; --O--COR.sup.29 ; 
##STR16## 
or --(CH.sub.2).sub.n --A'. R.sup.25 represents a hydrogen atom, an alkyl 
group or an aryl group; and R.sup.26 and R.sup.27 each independently 
represents a hydrogen atom, an alkyl group or an aryl group, or they may 
be joined together to form a five or six membered ring. R.sup.28 
represents a hydrogen atom or methyl group. R.sup.29 represents an alkyl 
group or an aryl group; and R.sup.30' and R.sup.31' each independently 
represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic 
group or an aralkyl group, or they may be joined together to form a five 
or six membered heterocyclic ring which has optional substituents as 
described earlier. 
A' represents an ester group or 
##STR17## 
Moreover, m and n represent integers of from 1 to 3. 
##STR18## 
In this formula, R.sup.8 preferably represents a hydrogen atom; a linear or 
branched chain alkyl group which has from 1 to 22 carbon atoms (for 
example, methyl, ethyl, t-butyl, t-octyl, i-propyl, t-pentyl, t-hexyl, 
n-octadecyl, 3-methyl-3-pentyl, 3-ethyl-3pentyl); or a linear or branched 
chain alkenyl group which has from 3 to 22 carbon atoms (for example, 
allyl, 1-t-butyl-1-allyl). R.sup.9 preferably represents a linear or 
branched chain alkyl group which has from 1 to 22 carbon atoms (for 
example, methyl, ethyl, t-butyl, t-octyl, i-propyl, t-pentyl, t-hexyl, 
n-octadecyl, 3-methyl-3-pentyl, 3-ethyl-3-pentyl); or a linear or branched 
chain alkenyl group which has from 3 to 22 carbon atoms (for example, 
allyl, 1-t-butyl-1-allyl), and R.sup.8 and R.sup.9 may be the same or 
different. Furthermore, R.sup.1 has the same significance as R.sup.1 in 
general formula [I]. 
Furthermore, either of the above-mentioned substituents R.sup.8 and R.sup.9 
may have an --NHCO-- bond within the group. 
##STR19## 
In the formula, R.sup.10 represents an alkyl group (for example, methyl, 
ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl); an alkenyl group 
(for example, allyl, octenyl, oleyl); an aryl group (for example, phenyl, 
naphthyl); an aralkyl group (for example, benzyl); a heterocyclic group 
(for example, tetrahydropyranyl, pyrimidyl); or a group which can be 
represented by R.sup.18 CO, R.sup.19 SO.sub.2 or R.sup.20 NHCO. Here, 
R.sup.18, R.sup.19 and R.sup.20 each represents an alkyl group (for 
example, methyl, ethyl, n-propyl, n-butyl, n-octyl, tert-octyl, benzyl); 
an alkenyl group (for example, allyl, octenyl, oleyl); an aryl group (for 
example, phenyl, methoxyphenyl, naphthol); or a heterocyclic group (for 
example, pyridyl, pyrimidyl). R.sup.11 and R.sup.12 each represents a 
hydrogen atom; a halogen atom (for example, fluorine, chlorine, bromine); 
an alkyl group (for example, methyl, ethyl, n-butyl, benzyl); an alkenyl 
group (for example, allyl, hexenyl, octenyl); an alkoxy group (for 
example, methoxy, ethoxy, benzyloxy); or an alkenoxy group (for example, 
2-propenyloxy, hexenyloxy). R.sup.13, R.sup.14, R.sup.15, R.sup.16 and 
R.sup.17 independently represent hydrogen atoms; alkyl groups (for 
example, methyl, ethyl, n-butyl, benzyl); alkenyl groups (for example, 
2-propenyl, hexenyl, octenyl); or aryl groups (for example, phenyl, 
methoxyphenyl, chlorophenyl, naphthyl). 
##STR20## 
In this formula, B represents a group of non-metal atoms which, together 
with the adjacent atoms, forms a five to seven membered ring (for example, 
depending on B, the ring which is formed may be a pyrrolidine ring, 
piperazine ring, morpholine ring or a piperidine ring). R.sup.30 
represents a hydrogen atom; an alkyl group (for example, methyl, ethyl, 
n-octyl, benzyl, hexadecyl); an alkenyl group (for example, allyl, oleyl); 
an alkynyl group (for example, ethynyl, propynyl); an acyl group (for 
example, acetyl, benzoyl, pentanoyl); a sulfonyl group (for example 
methanesulfonyl, benzenesulfonyl, toluenesulfonyl, hexadecanesulfonyl); a 
sulfinyl group (for example, methanesulfinyl, benzenesulfinyl, 
butanesulfinyl); an oxy radical group; or hydroxyl group. R.sup.31, 
R.sup.32, R.sup.33 and R.sup.34 may be the same or different, each 
representing a hydrogen atom or an alkyl group (for example, methyl, 
ethyl, butyl). 
The formation of a piperidine ring by B is preferred and, most desirably, a 
piperidine ring is formed by B and at least two of R.sup.31, R.sup.32, 
R.sup.33 and R.sup.34 are methyl groups. 
Actual examples of compounds represented by the general formulae [I] to 
[V], including those represented by general formulae [I'] and [II'], which 
can be used in the invention are indicated below, but the invention is not 
limited to these examples. 
##STR21## 
Just one of the chroman based compounds or coumaran based compounds 
represented by the general formula [I], the phenol based derivatives 
represented by the general formula [II], or the hydroquinone based 
derivatives represented by general formula [III], or the spiroindane based 
derivatives represented by the general formula [IV] or the hindered amine 
based derivatives represented by general formula [V] can be used, or two 
or more of these compounds can be used conjointly. Moreover, they can be 
used conjointly with antioxidants and anti-color fading agents other than 
those represented by the general formulae [I] to [V], [I'] and [II']. 
Moreover, use can also be made, as anti-color fading agents, of the 
hydroquinone derivatives disclosed, for example, in U.S. Pat. Nos. 
2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,639, 
2,732,300, 2,735,765, 2,710,801 and 2,816,028 and British Patent 
1,363,921; the gallic acid derivatives disclosed, for example, in U.S. 
Pat. Nos. 3,457,079 and 3,069,262; the p-alkoxyphenols disclosed in U.S. 
Pat. Nos. 2,735,765 and 3,698,909, JP-B-49-20977 and JP-B-52-6623; and the 
p-oxyphenol derivatives disclosed in U.S. Pat. Nos. 3,432,300, 3,573,050, 
3,574,627 and 3,764,337, JP-A-52-35633, JP-A-52-14743 and JP-A-52-152225, 
for example. (The term "JP-B" as used herein means an "examined Japanese 
Patent Publication".) 
Furthermore, compounds suitable for anti-fading use can be selected from 
among a certain variety of metal complexes. The preferred metal complexes 
are chelate complexes which have at least one ligand selected from among 
the 1 to 4 coordinate ligands. Actual embodiments of these chelating 
complexes include those coordinated with two bidentate ligands, those 
coordinated with one tridentate ligand and one unidentate ligand, and 
those coordinated with a single tetradentate ligand. 
Nitrogen, oxygen, sulfur and halogen (for example, chlorine, bromine, 
iodine) atoms are the preferred coordinating atoms. 
The transition metals, which is to say the metals from scandium, atomic 
number 21, to zinc, atomic number 30; from yttrium, atomic number 39 to 
cadmium, atomic number 48; from lanthanum, atomic number 57, to mercury, 
atomic number 80; and those of atomic number 89 (actinium) or above are 
effective as the metal which is required in the complex. Among these 
metals, copper, cobalt, nickel, palladium and platinum are preferred. 
Metal complexes wherein the complex (complex group) as a whole forms an 
anion, or in which the electrical charge is neutralized within the 
complex, are preferred. The counter cation when an anionic complex is 
formed is preferably a univalent or divalent cation. 
Univalent and divalent cations include, for example, alkali metal ions 
(LI.sup.+, Na.sup.+, K.sup.+), alkaline earth metal ions (Mg.sup.2+, 
Ca.sup.2+, Sr.sup.2+, Ba.sup.2+), bis-onium ions (bisammonium ion or 
bisphosphonium ion), and onium ions (quaternary ammonium ion, quaternary 
phosphonium ion, tertiary sulfonium ion). 
Transition metal complexes are themselves often colored with a peak 
absorption in the visible wavelength band, but when they are colored this 
can give rise to staining of the dye fixing layer and so the anti-color 
fading agents which are included in the dye fixing layer are preferably 
colorless, or substantially colorless compounds. 
The metal complexes represented by the general formulae (1-I), (2-I) to 
(2-IV), (3-I) and (3-II) below are colorless or substantially colorless 
anti-color fading agents. 
##STR22## 
In formula (1-I) above, M.sub.1 is Cu, Co, Ni, Pd or Pt; X is 0 or S, 
R.sub.11 represents an alkyl group, an aryl group, an alkoxy group or an 
aryloxy group, provided that the R.sub.11 groups which are bonded to the 
same phosphorus atom may be joined together to form, together with the 
phosphorus atom, a six membered ring. 
Details of these complexes have been disclosed in columns 3 to 6 of the 
specification of U.S. Pat. No. 4,241,155, and the compounds indicated 
below are specific examples of such complexes. 
##STR23## 
In formulae (2-I) to (2-IV) above, M.sub.2 has the same significance as 
M.sub.1. R.sup.12', R.sup.22', R.sup.32' and R.sup.42 each independently 
represent a hydrogen atom, halogen atom, cyano group, alkyl group, aryl 
group, cycloalkyl group or heterocyclic group, and these atoms or groups 
are bonded to carbon atoms on the benzene rings either directly or via 
divalent linking groups. 
R.sup.12' and R.sup.22', R.sup.22' and R.sup.32', or R.sup.32' and 
R.sup.42, may be jointed together to form a six membered ring. 
R.sup.52 and R.sup.82 each independently represents a hydrogen atom, alkyl 
group or aryl group. 
R.sup.62 represents a hydrogen atom, alkyl group, aryl group or hydroxyl 
group. 
R.sup.72 represents an alkyl group or aryl group. Z represents a group of 
non-metal atoms required to form a five or six membered ring. 
Details of these metal complexes have been disclosed in columns 3 to 36 of 
the specification of U.S. Pat. No. 4,245,018, and the compounds indicated 
below are specific examples of these complexes. 
##STR24## 
In formulae (3-I) and (3-II) above, M.sub.3 has the same significance as 
M.sub.1 in general formula (1-I), and R.sup.13', R.sup.23', R.sup.33' and 
R.sup.43 have the same significance as R.sup.12', R.sup.22', R.sup.32' and 
R.sup.42 in general formulae (2-I) to (2-IV), respectively. R.sup.53 and 
R.sup.63 each independently represent a hydrogen atom, alkyl group, aryl 
group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, 
alkylsulfonyl group or arylsulfonyl group. 
Details of these complexes have been disclosed in columns 3 to 8 of the 
specification of U.S. Pat. No. 4,254,195, and the compounds indicated 
below are specific examples of these complexes. 
##STR25## 
In these formulae, [Cat.sub.1 ] and [Cat.sub.2 ] indicate cations which are 
needed to neutralize the complex, and M.sub.4 has the same significance as 
M.sub.1. Moreover, n.sub.1 represents 1 or 2. 
##STR26## 
Here, [Cat] represents a cation which is needed to neutralize the complex, 
n.sub.1 represents 1 or 2, and M.sub.4 has the same significance as 
M.sub.1. 
R.sup.91 represents a substituted or unsubstituted alkyl group, aryl group 
or heterocyclic group, and the two R.sup.91 groups attached to the same 
ligand can be joined together to form a ring. 
Details of these compounds have been disclosed in JP-A-62-174741, and the 
compounds indicated below are specific examples of these compounds. 
##STR27## 
In formula (5-I), R.sup.101 to R.sup.104 each independently represents a 
hydrogen atom, halogen atom, cyano group, hydroxyl group, an alkyl group 
which is bonded directly, or indirectly via a divalent linking group, to a 
carbon atom of the pyridine ring, aryl group, cycloalkyl group or 
heterocyclic group, and these groups may be the same or different. 
Furthermore, two adjacent groups from among R.sup.101 to R.sup.104 can be 
joined together to from a ring. Furthermore, the two R.sup.104 groups may 
be joined together to form a ring. 
R.sup.105 and R.sup.106 independently represent hydrogen atoms, alkyl 
groups, alkylthio groups, aryl groups, arylthio groups, heterocyclic thio 
groups or cyano groups, and they may be the same or different, and 
R.sup.105 and R.sup.106 may be joined together to form a ring. 
##STR28## 
In these formulae, R.sup.107 to R.sup.111 independently represent halogen 
atoms, hydrogen atoms, alkyl groups which are bonded directly, or 
indirectly via a divalent linking group, to a carbon atom of the benzene 
ring, aryl groups, cycloaklyl groups or heterocyclic groups, and they may 
be the same or different. Furthermore, adjacent substituents among these 
groups can be joined together to form a ring. R.sup.112 and R.sup.113 
independently represent alkyl groups or aryl groups, and these may be the 
same or different. R.sup.114 and R.sup.115 represent hydrogen atoms, alkyl 
groups, aryl groups or cyano groups and they may be the same or different, 
or R.sup.114 and R.sup.115 may be joined together to form a ring. 
Details of general formula (5-I) have been disclosed in JP-A-63-199248. The 
compounds indicated below are specific examples of these compounds. 
##STR29## 
In these formulae, M.sub.6 has the same significance as M.sup.1, X and X' 
each independently represents a member selected from the group consisting 
of sulfur and oxygen, and Cat.sup.+ represents a cation. A.sub.1 
represents a group which can be represented by the following formulae: 
##STR30## 
In these formulae, R.sup.120 represents a hydrogen atom or alkyl group, and 
R.sup.121 and R.sup.122 each independently represents a hydrogen atom, 
phenyl group, substituted phenyl group, nitrile group and an alkyl group. 
Details of these compounds have been disclosed in JP-A-50-87649, and the 
compounds indicated below are specific examples of these compounds. 
##STR31## 
The compounds of this invention can be used conjointly with other 
antioxidants and ultraviolet absorbers. 
The ultraviolet absorbers include benzotriazole based compounds (for 
example, those described in U.S. Pat. No. 3,533,794); 4-thiazolidone based 
compounds (for example, those described in U.S. Pat. No. 3,352,681); 
benzophenone based compounds (for example, those described in 
JP-A-46-2784); and other compounds as disclosed, for example, in 
JP-A-54-48535, JP-A-62-136641 and JP-A-61-88256. The ultraviolet absorbing 
polymers disclosed in JP-A-62-260152 are also effective. 
Photosensitive elements of this invention comprise basically photosensitive 
silver halides, binders, and dye providing substances provided on a 
support. They can also contain organometallic salt oxidizing agents, etc. 
as required. These components are often added to the same layer, but if 
they are reactive they can be added separately to different layers. For 
example, if colored dye providing compounds are present below the silver 
halide emulsion layer, then reduction of photographic speed is prevented. 
The incorporation of reducing agents into the photosensitive element is 
preferred, but they may be provided from an external source, using, for 
example, the method of diffusion from the dye fixing element described 
hereinafter. 
Combinations of at least three silver halide emulsion layers which are 
photosensitive to different regions of the spectrum are used to obtain a 
wide range of colors in the chromaticity diagram using the three colors 
yellow, magenta and cyan. For example, there are three layer combinations 
consisting of a blue sensitive layer, a green sensitive layer and a red 
sensitive layer, and combinations consisting of a green sensitive layer, a 
red sensitive layer and an infrared sensitive layer. 
The photosensitive layers can be arranged in the various sequences known 
for the ordinary types of color photosensitive material. 
Furthermore, each of these photosensitive layers may be divided into two or 
more layers, as required. 
Various auxiliary layers, such as protective layers, subbing layers, 
interlayers, yellow filter layers, anti-halation layers and backing layers 
for example, can be established in the photosensitive element. 
The silver halide which may be used in the present invention may be any of 
silver chloride, silver bromide, silver iodobromide, silver chlorobromide, 
silver chloroiodide and silver chloroiodobromide. 
The silver halide emulsion used in the present invention may be a surface 
latent image type emulsion or an internal latent image type emulsion. The 
internal latent image type emulsion may be used as a direct reversal 
emulsion in combination with a nucleating agent or a light fogging agent. 
Alternatively, the silver halide emulsion may be a core/shell emulsion in 
which the interior and the surface of the grain are different from each 
other in phase. The silver halide emulsion may be a monodisperse or 
polydisperse emulsion or a mixture thereof. The grain size of the emulsion 
is preferably in the range of from 0.1 to 2 .mu.m, particularly from 0.2 
to 1.5 .mu.m. The crystal habit of the silver halide grains may be cubic, 
octahedral, tetradecahedral or tabular with a high aspect ratio. 
In particular, photosensitive silver halide emulsions as described in U.S. 
Pat. Nos. 4,500,626 and 4,628,021, Research Disclosure, No. 17029 (1978), 
and JP-A-62-253159 may be used in the present invention. 
The silver halide emulsion may be used unripened but is normally used after 
being chemically sensitized. For emulsions for the photosensitive 
materials, known sulfur sensitization processes, reduction sensitization 
processes and noble metal sensitization processes may be used singly or in 
combination. These chemical sensitization processes may be optionally 
effected in the presence of a nitrogen-containing heterocyclic compound as 
disclosed in JP-A-62-253159. 
The amount of the photosensitive silver halide emulsion coated is in the 
range of from 1 mg to 10 g/m.sup.2 (calculated in terms of amount of 
silver). 
The silver halide used in the present invention may be conventionally 
spectrally sensitized with a methine dye or the like. Examples of such 
dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex 
merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes 
and hemioxonol dyes. 
Specific examples of dyes include sensitizing dyes as described in U.S. 
Pat. No. 4,617,257, JP-A-59-180550, JP-A-60-140335, and Research 
Disclosure, No. 17029 (1978), pp. 12-13. 
These sensitizing dyes may be used singly or in combination. In particular, 
combinations of sensitizing dyes are often used for the purpose of 
supersensitization. 
The photosensitive silver halide emulsion may comprise a dye which does not 
exhibit a spectral sensitizing effect by itself or a compound which does 
not substantially absorb visible light but exhibits a supersensitizing 
effect (as described in U.S. Pat. No. 3,615,641 and JP-A-63-23145) 
together with such a sensitizing dye. 
Such sensitizing dyes may be incorporated in the emulsion during, before or 
after chemical sensitization. Alternatively, the sensitizing dye may be 
incorporated in the emulsion before or after the nucleation of 
photosensitive silver halide grains as described in U.S. Pat. Nos. 
4,183,756 and 4,225,666. The amount of sensitizing dye incorporated is 
normally in the range of from 10.sup.-8 to 10.sup.-2 mol per mol of 
photosensitive silver halide. 
In the present invention, organometallic salts may be used as oxidizing 
agents in combination with the photosensitive silver halide. Among such 
organometallic salts, organic silver salts are particularly preferably 
used. 
Examples of organic compounds which can be used to form such an organic 
silver salt oxidizing agent include benzotriazoles, fatty acids, and other 
compounds as described in U.S. Pat. No. 4,500,626 (52nd column to 53rd 
column). Other useful examples of such organic compounds include 
carboxylic acid silver salts containing an alkynyl group such as silver 
phenylpropiolate as described in JP-A-60-113235, and silver acetylide as 
described in JP-A-61-249044. These organic silver salts may be used in 
combination. 
These organic silver salts are generally used in an amount of from 0.01 to 
10 mols, preferably from 0.01 to 1 mol, per mol of photosensitive silver 
halide. The total amount of photosensitive silver salt and organic silver 
salt coated is preferably in the range of from 50 mg to 10 g/m.sup.2 
(calculated in terms of amount of silver). 
In the present invention, various fog inhibitors or photographic 
stabilizers may be used. Examples of such fog inhibitors or photographic 
stabilizers include azoles or azaindenes as described in Research 
Disclosure, No. 17643 (1978), pp. 24-25, nitrogen-containing carboxylic 
acids or phosphoric acids as described in JP-A-59-168442, mercapto 
compounds and metal salts thereof as described in JP-A-59-111636, and 
acetylenic compounds as described in JP-A-62-87957. 
As suitable reducing agents for the present invention there may be used 
conventional reducing agents known in the field of heat developable 
photosensitive materials. Alternatively, reducing dye-providing compounds 
as described later may be used. These reducing dye-providing compounds may 
be used in combination with other reducing agents. Further, a reducing 
agent precursor which does not exhibit a reducing effect but undergoes 
reaction with a nucleophilic reagent or under heating to exhibit a 
reducing effect may be used in the present invention. 
Examples of reducing agents used in the present invention include reducing 
agents or reducing agent precursors as described in U.S. Pat. No. 
4,500,626 (49th column to 50th column), U.S. Pat. No. 4,483,914 (30th 
column to 31st column), U.S. Pat. Nos. 4,330,617, and 4,590,152, 
JP-A-60-140335, JP-A-57-40245, JP-A-56-138736, JP-A-59-178458, 
JP-A-59-53831, JP-A-59-182449, JP-A-59-182450, JP-A-60-119555, 
JP-A-60-128436, JP-A-60-128437, JP-A-60-128438, JP-A-60-128439, 
JP-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-244044, 
JP-A-62-131253, JP-A-62-131254, JP-A-62-131255, and JP-A-62-131256, and 
European Patent 220,746A2 (pp. 78-96). 
Combinations of various reducing agents as disclosed in U.S. Pat. No. 
3,039,869 may also be used in the present invention. 
If a non-diffusible reducing agent is used, an electron transfer agent 
and/or electron transfer agent precursor may optionally be used in 
combination therewith in order to accelerate the transfer of electrons 
between the non-diffusible reducing agent and the developable silver 
halide. 
Such an electron transfer agent or its precursor may be selected from the 
above described reducing agents or precursors thereof. Such an electron 
transfer agent or its precursor is preferably greater than the 
non-diffusible reducing agent (electron donor) in mobility. Particularly 
useful electron transfer agents are 1-phenyl-3-pyrazolidones or 
aminophenols. 
As non-diffusible reducing agents (electron donors) used in combination 
with such an electron transfer agent there may be used any of the above 
described reducing agents which are substantially non-diffusible in the 
layer of photosensitive element in which they are located. Preferred 
examples of such non-diffusible reducing agents include hydroquinones, 
sulfonamidophenols, sulfonamidonaphthols, compounds described as electron 
donors in JP-A-53-110827, and non-diffusible reducing dye-providing 
compounds as later described. 
In the present invention, the amount of such reducing agent(s) incorporated 
is preferably in the range of from 0.001 to 20 mols, particularly from 
0.01 to 10 mols per mol of total silver. 
In the present invention, as an image-forming substance, a compound which 
produces or releases a mobile dye in correspondence or counter 
correspondence to the reduction of silver ions to silver, i.e., 
dye-providing compounds, may be incorporated in the photosensitive 
material. 
Examples of such dye-providing compounds which may be used in the present 
invention include compounds which undergo an oxidation coupling reaction 
with a color developing agent to form a dye (coupler). Such a coupler may 
be a two-equivalent coupler or four-equivalent coupler. A two-equivalent 
coupler containing a nondiffusible group as a split-off group which 
undergoes oxidation coupling reaction to form a diffusible dye is 
preferably used. Specific examples of suitable developing agents and 
couplers are described in T. H. James, The Theory of the Photographic 
Process, pp. 291-334 and 354-361, JP-A-58-123533, JP-A-58-149046, 
JP-A-58-149047, JP-A-59-111148, JP-A-59-124399, JP-A-59-174835, 
JP-A-59-231539, JP-A-59-231540, JP-A-60-2950, JP-A-60-2951, JP-A-60-14242, 
JP-A-60-23474, and JP-A-60-66249. 
Examples of different dye-providing compounds include compounds which 
serves to imagewise release or diffuse a diffusible dye. Such a compound 
can be represented by the following general formula (LI): 
EQU (Dye--Y).sub.n --Z (LI) 
wherein Dye represents a dye group, a dye group which has been temporarily 
shifted to a short wavelength range or a dye precursor group; Y represents 
a mere bond or connecting group; Z represents a group which makes a 
difference in the diffusibility of the compound represented by 
(Dye--Y).sub.n --Z in corresponding or counter-corresponding to 
photosensitive silver salts having a latent image distributed imagewise or 
releases Dye in corresponding or counter-corresponding to photosensitive 
silver salts having a latent image distributed imagewise to make no 
difference in the diffusibility between Dye thus released and 
(Dye--Y).sub.n --Z; and n represents an integer of 1 or 2. If n is 2, two 
(Dye--Y)'s may be the same or different. 
Specific examples of the dye-providing compound represented by the general 
formula (LI) include the following compounds i to v. The compounds i to 
iii form a diffusible dye image (positive dye image) in 
counter-corresponding to the development of silver halide while the 
compounds iv and v form a diffusible dye image (negative dye image) in 
corresponding to the development of silver halide. 
i. Dye developing agents comprising a hydroquinone developing agent 
connected to a dye component as described in U.S. Pat. No. 3,134,764, 
3,362,819, 3,597,200, 3,544,545, and 3,482,972. These dye developing 
agents are diffusible in alkaline conditions but become nondiffusible upon 
reaction with silver halide. 
ii. Nondiffusible compounds which release a diffusible dye in alkaline 
conditions but lose their function upon reaction with silver halide as 
described in U.S. Pat. No. 4,503,137. Examples of such compounds include 
compounds which undergo intramolecular nucleophilic displacement reactions 
to release a diffusible dye as described in U.S. Pat. No. 3,980,479, and 
compounds which undergo an intramolecular rewinding reaction of the 
isooxazolone ring to release a diffusible dye as described in U.S. Pat. 
No. 4,199,354. 
iii. Nondiffusible compounds that react with a reducing agent left 
unoxidized after being developed to release a diffusible dye as described 
in U.S. Pat. No. 4,559,290, European Patent 220,746A2, and Kokai Giho 
87-6,199. 
Examples of such compounds include compounds which undergo intramolecular 
nucleophilic displacement reaction after being reduced to release a 
diffusible dye as described in U.S. Pat. Nos. 4,139,389 and 4,139,379, and 
JP-A-59-185333, and JP-A-57-84453, compounds which undergo an 
intramolecular electron transfer reaction after being reduced to release a 
diffusible dye as described in U.S. Pat. No. 4,232,107, JP-A-59-101649, 
JP-A-61-88257, and Research Disclosure, No. 24,025 (1984), compounds which 
undergo cleavage of a single bond after being reduced to release a 
diffusible dye as described in West German Patent 3,008,588A, 
JP-A-56-142530, and U.S. Pat. Nos. 4,343,893, and 4,619,884, nitro 
compounds which receive electrons to release a diffusible dye as described 
in U.S. Pat. No. 4,450,223, and compounds which receive electrons to 
release a diffusible dye as described in U.S. Pat. No. 4,609,610. 
Preferred examples of such compounds include compounds containing an N13 X 
bond (wherein X represents oxygen atom, sulfur atom or nitrogen atom) and 
an electrophilic group in one molecule as described in European Patent 
220,746A2, Kokai Giho 87-6,199, JP-A-63-201653, and JP-63-201654, 
compounds containing an SO.sub.2 --X group (wherein X is as defined above) 
and an electrophilic group in one molecule as described in U.S. 
application Ser. No. 07/188,779, compounds containing a PO--X bond 
(wherein X is as defined above) and an electrophilic group in one molecule 
as described in JP-A-63-271344, and compounds containing a C--X' bond 
(wherein X' is as defined above for X or represent --SO.sub.2 --) and an 
electrophilic group in one molecule as described in JP-A-63-271341. 
Particularly preferred among these compounds are compounds containing an 
N--X bond and an electrophilic group in one molecule. Specific examples of 
such compounds include Compounds (1) to (3), (7) to (10), (12), (13), 
(15), (23) to (26), (31), (32), (35), (36), (40), (41), (44), (53) to 
(59), (64), and (70) described in European Patent 220,746A2, and Compounds 
(11) to (23) described in Kokai Giho 87-6,199. 
iv. Couplers containing a diffusible dye as the split-off group which 
reacts with an oxidation product of a reducing agent to release a 
diffusible dye (DDR coupler). Specific examples of such compounds include 
those described in British Patent 1,330,524, JP-B-48-39165, and U.S. Pat. 
Nos. 3,443,940, 4,474,867, and 4,483,914. 
v. Compounds which are capable of reducing silver halide or organic silver 
salts and release a diffusible dye after reducing silver halide or organic 
silver salts (DDR compound). These compounds are advantageous in that they 
need no other reducing agents. They eliminate image staining due to the 
action of oxidation decomposition products of reducing agents. Typical 
examples of such compounds are described in U.S. Pat. Nos. 3,928,312, 
4,053,312, 4,055,428, 4,336,322, 3,725,062, 3,728,113, 3,443,939, and 
4,500,626, JP-A-59-65839, JP-A-59-69839, JP-A-53-3819, JP-A-51-104343, 
JP-A-58-116537, JP-A-57-179840, and Research Disclosure, No. 17,465. 
Specific examples of DRR compounds include compounds as described in U.S. 
Pat. No. 4,500,626, 22nd column to 44th column, and particularly preferred 
among these compounds are compounds (1) to (3), (10) to (13), (16) to 
(19), (28) to (30), (33) to (35), (38) to (40), and (42) to (64). Other 
preferred examples of such compounds include those described in U.S. Pat. 
No. 4,639,408, 37th column to 39th column. 
Examples of dye-providing compounds other than the above described couplers 
and compounds of the general formula [LI] include silver halide dye 
compounds comprising an organic silver salt connected to a dye as 
described in Research Disclosure (May 1978, pp. 54-58), azo dyes for use 
in heat developable silver dye bleaching processes as described in U.S. 
Pat. No. 4,235,957 and Research Disclosure (April 1976, pp. 30-32), and 
leuco dyes as described in U.S. Pat. Nos. 3,985,565 and 4,022,617. 
The incorporation of a hydrophobic additive such as a dye-providing 
compound or a non-diffusible reducing agent in a layer of photosensitive 
element can be accomplished by any known method as described in U.S. Pat. 
No. 2,322,027. In this case, a high boiling organic solvent as described 
in JP-A-59-83154, JP-A-59-178451, JP-A-59-178452, JP-A-59-178453, 
JP-A-59-178454, JP-A-59-178455, and JP-A-59-178457 may optionally be used 
in combination with a low boiling organic solvent having a boiling point 
of from 50.degree. to 160.degree. C. 
The amount of such a high boiling organic solvent incorporated is generally 
in the range of from 1 to 10 g, preferably 5 g or less, per gram of 
dye-providing compound used or 1 cc or less, preferably 0.5 cc or less, 
particularly preferably 0.3 cc or less, per gram of binder. 
A dispersion process as described in JP-B-51-39853 and JP-A-51-59943 which 
comprises using a polymerization produce may also be used. 
If a compound which is substantially insoluble in water is used, it may be 
incorporated in the binder in the form of dispersion of finely divided 
particles rather than by the above described processes. 
In order to disperse a hydrophobic compound in a hydrophilic cooloid, 
various surface active agents can be used. Examples of such surface active 
agents which may be used in this dispersion process include those 
described as surface active agent in JP-A-59-157636 (pp. 37-38). 
In the present invention, a compound which serves both to accelerate the 
development of photosensitive materials and stabilize images may be used. 
Specific examples of such compounds preferably used in the present 
invention are described in U.S. Pat. No. 4,500,626 (51st column to 52nd 
column). 
In a system where the diffusion transfer of a dye(s) is used to form 
images, a dye fixing element is used in combination with the 
photosensitive element. Such a dye fixing element may be either coated on 
a separate support from the photosensitive element or coated on the same 
support as the photosensitive element. For the relationship of the 
photosensitive element with the dye fixing element, the support and a 
white reflecting layer which can be used, those described in U.S. Pat. No. 
4,500,626 (57th column) are useful. 
The dye fixing element preferably used in the present invention may 
comprise at least one layer containing a mordant and a binder. As such 
mordants there may be used those known in the field of photography. 
Specific examples of such mordants include those described in U.S. Pat. 
No. 4,500,626 (58th column to 59th column), JP-A-61-88256 (pp. 32-41), 
JP-A-62-244043 and JP-A-62-244036. Alternatively, a dye-receiving high 
molecular weight compound as described in U.S. Pat. No. 4,463,079 may be 
used. 
The dye fixing element may optionally comprise auxiliary layers such as a 
protective layer, strippable layer or anti-curling layer. Particularly, a 
protective layer can be advantageously incorporated in the dye fixing 
element. 
As suitable binders incorporated in the photosensitive element or dye 
fixing element there may be used a hydrophilic binder. Examples of such 
hydrophilic binders include those described in JP-A-62-253159 (pp. 26-28). 
Specific examples of such hydrophilic binder include transparent or 
semi-transparent hydrophilic binders such as proteins (e.g., gelatin, 
gelatin derivative), polysaccharides (e.g., cellulose derivatives, starch, 
gum arabic, dextran, pullulan), and synthetic high molecular compounds 
(e.g., polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers). 
Alternatively, a high water-absorbing polymer as described in 
JP-A-62-245260, i.e., a homopolymer of a vinyl monomer containing --COOM 
or --SO.sub.3 M (wherein M represents a hydrogen atom or alkali metal) or 
a copolymer of such vinyl monomers or such a vinyl monomer with other 
vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, 
SUMIKAGEL.RTM. L-5H made by Sumitomo Chemical Co., Ltd.) may be used. 
These binders may be used singly or in combination. 
In a system wherein heat development is effected with a slight amount of 
water, the above described high water-absorbing polymer may be used to 
expedite the absorption of water. Such a high water-absorbing polymer may 
be incorporated in the dye fixing layer or in a protective layer therefor 
to prevent dye which has been transferred from being re-transferred from 
the dye fixing element to other elements. 
In the present invention, the amount of the binder coated is preferably in 
the range of 20 g or less, more preferably 10 g or less, particularly 7 g 
or less per m.sup.2. 
Example of film hardeners which may be incorporated in the constituent 
layers of the photosensitive element or dye fixing element include those 
described in U.S. Pat. No. 4,678,739 (41st column), JP-A-59-116655, 
JP-A-62-245261, and JP-A-61-18942. Specific examples of such film 
hardeners include aldehyde film hardeners (e.g., formaldehyde), aziridene 
film hardeners, epoxy film hardeners (e.g., 
##STR32## 
vinylsulfone film hardeners (e.g., 
N,N'-ethylenebis(vinylsulfonylacetamido)ethane), N-methylol film hardeners 
(e.g., dimethylol urea), and high molecular film hardeners (e.g., 
compounds as described in JP-A-62-234157), 
In the present invention, the photosensitive element and/or dye fixing 
element may include an image formation accelerator. Such an image 
formation accelerator serves to accelerate a redox reaction between a 
silver salt oxidizing agent and a reducing agent, accelerate production or 
decomposition of a dye from a dye providing compound or release of a 
diffusible dye from the dye providing compound, or accelerate transfer of 
a dye from a photosensitive material layer to a dye fixing layer. From the 
physicochemical standpoint, image formation accelerators can be classified 
into various groups such as base or base precursor, nucleophilic compound, 
high boiling organic solvent (oil), thermal solvent, surface active agent, 
and compounds capable of interacting with silver or silver ion. However, 
these groups normally have composite functions and therefore exhibit a 
combination of the above described accelerating effects. Details are given 
in U.S. Pat. No. 4,678,739 (38th column to 40th column). 
Examples of such base precursors include salts of an organic acid capable 
of being heat-decarboxylated with a base, and compounds which undergo an 
intramolecular nucleophilic displacement reaction, Lossen rearrangement or 
Beckman rearrangement to release an amine. Specific examples of such base 
precursors are described in U.S. Pat. No. 4,511,493 and JP-A-62-65038. 
In a system where heat development and dye transfer are simultaneously 
effected in the presence of a small amount of water, such a base and/base 
precursor may be preferably incorporated in the dye fixing element to 
improve the storage stability of the photosensitive element. 
Other examples of suitable base precursors include a combination of a 
sparingly soluble metallic compound and a compound capable of complexing 
with metal ions constituting said metallic compound as described in 
European Patent 210,660A, and a compound as described in JP-A-61-232451 
which undergoes electrolysis to produce a base. Particularly, the former 
compound may be effectively used. The sparingly soluble metallic compound 
and the complexing compound may advantageously be incorporated separately 
in the photosensitive element and the dye fixing element. 
The present photosensitive element and/or dye fixing element may comprise 
various development stopping agents for the purpose of providing images 
resistant against fluctuations in temperature and time for development. 
The term "development stopping agent" as used herein means a compound which 
readily neutralizes or reacts with a base to reduce the base concentration 
in the film to stopping development, or which interacts with silver or 
silver salt to inhibit development, after a proper development period. 
Specific examples of such compounds include acid precursors which release 
an acid on heating, electrophilic compounds which undergo a displacement 
reaction with a base present therewith on heating, and nitrogen-containing 
heterocyclic compounds, mercapto compounds and precursors thereof. 
Details are given in JP-A-62-253159 (pp. 31-32). 
The constituent layers (including the backing layer) of the photosensitive 
element or dye fixing element may comprise various polymer latexes for the 
purpose of dimensional stability, inhibiting curling, adhesion, film 
cracking and pressure sensitization or desensitization or improving other 
film properties. Specific examples of suitable polymer latexes which may 
be used include those described in JP-A-62-245258, JP-A- 62-136648, and 
JP-A-62-110066. In particular, if a polymer latex having a low glass 
transition point (40.degree. C. or lower) is incorporated in the mordant 
layer, cracking of the mordant layer can be prevented. If a polymer latex 
having a high glass transition point is incorporated in the backing layer, 
an anticurling effect can be provided. 
The constituent layers of the photosensitive element or dye fixing element 
may comprise a high boiling organic solvent as a plasticizer, lubricant or 
agent for improving the strippability of the photosensitive element from 
the dye fixing element. Specific examples of such a high boiling organic 
solvent include those described in JP-A-62-253159 (page 25) and 
JP-A-62-245253. 
For the above described purposes, various silicone oils ranging from 
dimethyl silicone oil to modified silicone oil obtained by incorporating 
various organic groups into dimethylcycloxane may be used. For example, 
various modified silicone oils, particularly carboxy-modified silicone 
(trade name: X-22-3710), described at pp. 6-8 of "Modified Silicone Oil", 
technical data reported by Shin-Etsu Silicone Co., Ltd., may be 
effectively used. 
Silicone oils as described in JP-A-62-215953 and JP-A-63-46449 may also be 
effectively used. 
The photosensitive element or dye fixing element may comprise a fluorescent 
brightening agent. In particular, such a fluorescent brightening agent may 
be incorporated in the dye fixing element or supplied into the dye fixing 
element from other elements such as photosensitive element. Examples of 
such fluorescent brightening agents include compounds as described in K. 
Veenkataraman, The Chemistry of Synthetic Dyes, Vol. V, Chapter 8, and 
JP-A-61-143752. Specific examples of such compounds include stilbene 
compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, 
naphthalimide compounds, pyrazoline compounds, and carbostyryl carboxy 
compounds. 
Such a fluorescent brightening agent may be used in combination with a 
discoloration inhibitor. 
The constituent layers of the photosensitive element or dye fixing element 
may comprise various surface active agents for the purpose of aiding of 
coating, improving strippability and lubricity, inhibiting static 
electrification or accelerating development. Specific examples of such 
surface active agents are described in JP-A-62-173463 and JP-A-62-183457. 
The constituent layers of the photosensitive element or dye fixing element 
may comprise an organofluoro compound for the purpose of improving 
lubricity and strippability or inhibiting static electrification. Typical 
examples of such an organofluoro compound include fluorine surface active 
agents as described in JP-B-57-9053 (8th column to 17th column), 
JP-A-61-20944, and JP-A-62-135826, and hydrophobic fluorine compounds such 
as oily fluorine compounds (e.g., fluorine oil) or solid fluorine compound 
resins (e.g., tetrafluoroethylene resin). 
The photosensitive element or dye fixing element may comprise a matt agent. 
Examples of such a matt agent include compounds as described in 
JP-A-61-88256 (pp. 29) (e.g., silicon dioxide, polyolefin, 
polymethacrylate) and compounds as described in JP-A-63-279944 and 
JP-A-63-274952 (e.g., benzoguanamine resin beads, polycarbonate resin 
beads, AS resin beads). 
Furthermore, the constituent layers of the photosensitive element or dye 
fixing element may comprise a thermal solvent, an anti-foaming agent, an 
anti-bacterial and anti-fungal agent or colloidal silica. Specific 
examples of these additives are described in JP-A-61-88256 (pp. 26-32). 
As a suitable support for the dye fixing element or photosensitive element, 
there may be used a material capable of withstanding the processing 
temperature. In general, paper or a synthetic high molecular weight 
compound (film) may be used. Specific examples of such a support material 
which may be used in the present invention include polyethylene 
terephthalate, polycarbonates, polyvinyl chloride, polystyrene, 
polypropylene, polyimides or celluloses (e.g., triacetyl cellulose) or a 
material obtained by incorporating a pigment such as titanium oxide in 
such a film, a synthetic paper film formed of polypropylene or the like, a 
mixed paper made of synthetic resin pulp such as polyethylene and natural 
pulp, Yankee paper, baryta paper, coated paper (particularly cast coat 
paper), metals, fabrics, and glass. 
Such a support material may be used as it is or in the form of a material 
laminated with a synthetic high molecular weight compound such as 
polyethylene on one or both sides thereof. 
Alternatively, a support material as described in JP-A-62-253159 (pp. 
29-31) may be used in the present invention. 
These support materials may be coated with a hydrophilic binder, a 
semiconducting metal oxide such as alumina sol or tin oxide, carbon black 
or other antistatic agents. 
Examples of process for exposing the photosensitive element to light for 
imaging include processes which comprise using a camera to photograph 
scenery or persons, processes which comprise using a printer or enlarger 
to expose the photosensitive material to light through a reversal film or 
negative film, processes which comprise using an exposing machine such as 
a copying machine to effect scanning exposure of the photosensitive 
material to an original through a slit, processes which comprise exposing 
the photosensitive material to light representative of image data emitted 
by a light emitting diode or various lasers, and processes which comprise 
exposing the photosensitive material directly or through an optical system 
to light representative of image data emitted by an image display 
apparatus such as a CRT, liquid crystal display, electroluminescence 
display or plasma display. 
As a light source for recording images on the photosensitive material there 
may be used natural light, tungsten lamp, a light emitting diode, a laser, 
a CRT or light sources as described in U.S. Pat. No. 4,500,626 (56th 
column). 
Furthermore, light of a wavelength where the wavelength of the light source 
has been modulated with a non-linear optical element can also be used. In 
this case, it is possible to obtain easily light of a wavelength in the 
blue region which previously had been difficult to obtain with laser light 
or LED's. 
Examples of image data which can be recorded on the present photosensitive 
material include picture signals from a video camera, electron still 
camera or the like, a television signal according to Nippon Television 
Signal Code (NTSC), a picture signal obtained by dividing an original into 
many pixels by means of a scanner or the like, and a picture signal 
produced by means of a CG, CAD or like computer. 
The heating temperature at which heat development can be effected is 
preferably in the range of from about 50.degree. C. to about 250.degree. 
C., particularly from about 80.degree. C. to about 180.degree. C. The dye 
diffusion transfer process may be effected simultaneously with or after 
heat development. In the latter case, the heating temperature at which dye 
transfer can be effected is preferably in the range of from the heating 
temperature for heat development to room temperature, particularly from 
50.degree. C. to a temperature about 10.degree. C. lower than the heating 
temperature for heat development. 
The transfer of a dye can be effected by heating alone. In order to 
accelerate the dye transfer, a solvent may be used. 
Alternatively, a process as described in JP-A-59-218443 and JP-A-61-238056 
which comprises heating the photosensitive material in the presence of a 
small amount of a solvent, particularly water, to effect development and 
dye transfer simultaneously or in sequence may be effectively used. The 
heating temperature for this process is preferably in the range of from 
50.degree. C. to a temperature not higher than the boiling point of the 
solvent. For example, if the solvent is water, the heating temperature is 
preferably in the range of from 50.degree. C. to 100.degree. C. 
Examples of a solvent which may be used to accelerate development and/or 
transfer of a diffusible dye to the dye fixing layer include water and a 
basic aqueous solution containing an inorganic alkali metal salt or 
organic base as described with reference to the image formation 
accelerators. Other useful examples of solvents include a low boiling 
solvent and a mixed solution made of such a low boiling solvent and water 
or a basic aqueous solution. Such a solvent may further comprise a surface 
active agent, fog inhibitor, sparingly soluble metal salt, complexing 
compound or the like. 
These solvents may be incorporated in either or both of the photosensitive 
element and the dye fixing element. The amount of the solvent incorporated 
in the photosensitive element and/or dye fixing element may be small such 
as not more than the weight of the solvent in a volume corresponding to 
the maximum swelling volume of the total coated films (particularly, not 
more than the value obtained by subtracting the weight of the entire 
coated film(s) from the weight of the solvent in a volume corresponding to 
the maximum swelling volume of the entire coated film(s)) in the 
photosensitive or dye fixing solvent. 
As the process for incorporating the solvent in the photosensitive layer or 
dye fixing layer, those described in JP-A-61-147244 (page 26) can be 
referenced. Alternatively, the solvent may be incorporated in either or 
both of the photosensitive element and the dye fixing element in a 
microcapsule form or like form. 
In order to accelerate transfer of a dye, a hydrophilic thermal solvent 
which stays solid at normal temperature but dissolves at an elevated 
temperature may be incorporated in the photosensitive element or dye 
fixing element. Such a hydrophilic thermal solvent may be incorporated in 
either or both of the photosensitive element and the dye fixing element. 
The layer in which the solvent is incorporated may be any one of emulsion 
layer, interlayer, protective layer and dye fixing layer, preferably the 
dye fixing layer and/or a layer adjacent thereto. 
Examples of such a hydrophilic thermal solvent include ureas, pyridines, 
amides, sulfonamides, imides, anisoles, oximes and other heterocyclic 
compounds. 
In order to accelerate the transfer of a dye, a high boiling organic 
solvent may be incorporated in the photosensitive element and/or dye 
fixing element. 
Examples of heating processes at development and/or the dye transfer step 
include processes which comprise bringing the photosensitive material into 
contact with a heated block or plate, processes which comprise bringing 
the photosensitive material into contact with a heating plate, hot 
presser, heat roller, halogen lamp heater, infrared or far infrared lamp 
heater or the like, and processes which comprises passing the 
photosensitive material through a high temperature atmosphere. 
Alternatively, the photosensitive element or dye fixing element may be 
provided with a resistive heating element layer so that it is heated by 
passing an electric current through the resistive heating element layer. 
As such a resistive heating element layer there may be used the one 
described in JP-A-61-145544. 
As the pressure conditions and pressure application processes for the 
lamination of the photosensitive element and the dye fixing element, those 
described in JP-A-61-147244 (p. 27) can be used. 
For the photographic processing of the photographic element, any suitable 
heat developing apparatus may be employed. 
Examples of such a heat developing apparatus preferably used in the present 
invention include those described in JP-A-59-75247, JP-A-59-177547, 
JP-A-59-181353, JP-A-60-18951, and JP-A-U-62-25944 (the term "JP-A-U" as 
used herein means an "unexamined published Japanese utility model 
application"). 
EXAMPLE 1 
An image receiving material R-1 was prepared by coating with the various 
layers indicated in Table 1. Unless otherwise indicated, all parts, 
percents, ratios etc. are by weight. 
TABLE 1 
______________________________________ 
Structure of the Image Receiving Material R-1 
Amount 
Layer Number 
Materials Added (g/m.sup.2) 
______________________________________ 
Third Layer 
Gelatin 0.05 
Film hardening agent (2)* 
0.20 
Silicone oil (1)* 0.04 
Surfactant (1)* 0.001 
Surfactant (2)* 0.02 
Surfactant (3)* 0.10 
Matting agent (1)* 
0.02 
Guanidine picolinate 
0.45 
Water soluble polymer (1)* 
0.05 
Second Layer 
Mordant (1)* 2.0 
Water soluble polymer (1)* 
0.60 
Gelatin 0.7 
Water soluble polymer (2)* 
0.05 
High boiling point organic 
0.7 
solvent (1)* 
Guanidine picolinate 
1.80 
Surfactant (4)* 0.02 
First Layer 
Gelatin 0.45 
Surfactant (3)* 0.01 
Water soluble polymer (1)* 
0.04 
Film hardening agent (2)* 
0.80 
Support Polyethylene layer 
45 .mu.m 
Cast coat layer 10 .mu.m 
Coat layer 10 .mu.m 
Plain paper 60 .mu.m 
Coat layer 10 .mu.m 
Polyethylene layer 
35 .mu.m 
First Backing 
Gelatin 3.25 
Layer Film hardening agent (1)* 
0.25 
Second Backing 
Gelatin 0.44 
Layer Silicone oil (1)* 0.08 
Surfactant (4)* 0.05 
Matting agent (2)* 
0.09 
Surfactant (5)* 0.01 
______________________________________ 
Silicon Oil (1)* 
##STR33## 
Surfactant (1) 
##STR34## 
Surfactant (2)* 
##STR35## 
Surfactant (3)* 
##STR36## 
Surfactant (4)* 
##STR37## 
Surfactant (5)* 
##STR38## 
Water Soluble Polymer (1)* 
Poly(sodium methacrylate) 
Water Soluble Polymer (2)* 
Dextran (molecular weight: 70,000) 
Mordant (1)* 
##STR39## 
High Boiling Point Organic Solvent (1)* 
Rheophos .RTM. 95 (Made by Ajinomoto Co., Inc.) 
Film Hardening Agent (1)* 
##STR40## 
Film Hardening Agent (2)* 
1,3-Vinylsulfonyl-2-propanol 
Matting Agent (1)* 
Silica 
Matting Agent (2)* 
Benzoguanamine resin (average particle size: 15 .mu.m) 
*The high boiling point organic solvent was added as oil droplets. 
Five ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate were 
added to 100 grams of a 10% aqueous gelatin solution, 25 grams of 
Rheophos.RTM. 95 were added thereto and the dispersion of oil droplets 
obtained by emulsification and dispersion in a homogenizer at 10,000 rpm 
for a period of 6 minutes was added to the coating liquid for the dye 
fixing layer (second layer). 
Next, image receiving materials (R-2) to (R-6) were prepared in the same 
way as image receiving material (R-1) except that the compounds indicated 
below were included in the oil droplets in an amount of 0.5 g/m.sup.2. 
______________________________________ 
k.sub.q .multidot. T.sub.1 
k.sub.q .multidot. O.sub.2 
(M.sup.-1 .multidot. sec.sup.-1) 
(M.sup.-1 .multidot. sec.sup.-1) 
______________________________________ 
R-2 Compound II'-3 
2.6 .times. 10.sup.6 
8.0 .times. 10.sup.7 
R-3 Compound II'-7 
2.0 .times. 10.sup.5 
1.5 .times. 10.sup.7 
R-4 Compound II'-20 
3.5 .times. 10.sup.5 
2.3 .times. 10.sup.7 
R-5 Compound V-2 4.7 .times. 10.sup.8 
2.4 .times. 10.sup.8 
R-6 Compound 2-2 -- 3.4 .times. 10.sup.9 
______________________________________ 
Furthermore, an image receiving material (R-7) was prepared with the 
addition of 0.5 g/m.sup.2 of compound III-6 as an aqueous solution to the 
second layer. 
______________________________________ 
k.sub.q .multidot. T.sub.1 
k.sub.q .multidot. O.sub.2 
(M.sup.-1 .multidot. sec.sup.-1) 
(M.sup.-1 .multidot. sec.sup.-1) 
______________________________________ 
R-7 Compound III-6 
1.3 .times. 10.sup.6 
3.0 .times. 10.sup.7 
______________________________________ 
The preparation of the photosensitive materials was achieved in the way 
described below. 
Photosensitive material (K-1) was prepared by coating with the structure 
shown in Table 2 on a polyethylene terephthalate support. 
TABLE 2 
__________________________________________________________________________ 
Photosensitive Material (K-1) 
Amount 
Layer Number and Name 
Materials Added (g/m.sup.2) 
__________________________________________________________________________ 
Sixth Layer Gelatin 0.91 
(Protective Layer) 
Matting agent (silica) 0.03 
Water soluble polymer (1)* 
0.23 
Surfactant (1)* 0.06 
Surfactant (2)* 0.13 
Film hardening agent (1)* 
0.01 
ZnSO.sub.4.7H.sub.2 O 0.06 
Fifth Layer Emulsion (III) as silver 
0.58 
(Blue Sensitive Layer) 
Gelatin 0.68 
Sensitizing dye (2) 1.2 .times. 10.sup.-3 
Anti-fogging agent (2)* 1.36 .times. 10.sup.-3 
Yellow dye providing substance (1) 
0.50 
High boiling point organic solvent (1)* 
0.25 
Electron donor (ED-11) 0.25 
Surfactant (3)* 0.05 
Electron transfer agent (X-22) 
0.03 
Film hardening agent (1)* 
0.01 
Water soluble polymer (2)* 
0.02 
Fourth Layer Gelatin 0.75 
(Interlayer) Zn(OH).sub.2 0.32 
Reducing agent (ED-37) 0.11 
Surfactant (1)* 0.02 
Surfactant (4)* 0.07 
Water soluble polymer (2)* 
0.02 
Film hardening agent (1)* 
0.01 
Third Layer Emulsion (III) as silver 
0.41 
(Green Sensitive Layer) 
Gelatin 0.47 
Anti-fogging agent (1)* 1.25 .times. 10.sup.-3 
Magenta dye providing substance (2) 
0.37 
High boiling point organic solvent (1)* 
0.19 
Electron donor (ED-11) 0.14 
Surfactant (3)* 0.04 
Electron transfer agent (X-22) 
0.03 
Film hardening agent (1)* 
0.01 
Water soluble polymer (2)* 
0.02 
Second Layer Gelatin 0.80 
(Interlayer) Zn(OH).sub.2 0.31 
Reducing agent (ED-37) 0.11 
Surfactant (1)* 0.06 
Surfactant (4)* 0.10 
Water soluble polymer (2)* 
0.03 
Film hardening agent (1)* 
0.01 
First Layer Emulsion (I) as silver 0.36 
(Red Sensitive Layer) 
Gelatin 0.49 
Anti-fogging agent (1)* 1.25 .times. 10.sup.-3 
Cyan dye providing substance (3) 
0.37 
High boiling point organic solvent (1)* 
0.18 
Electron donor (ED-11) 0.14 
Surfactant (3)* 0.04 
Electron transfer agent (X-22) 
0.03 
Film hardening agent (1)* 
0.01 
Water soluble polymer (2)* 
0.02 
Support (Polyethylene terephthalate: Thickness 100 .mu.m) 
Backing Layer Carbon black 0.44 
Polyester 0.30 
Poly(vinyl chloride) 0.30 
__________________________________________________________________________ 
Water Soluble Polymer (1)* 
Sumikagel .RTM. L-5 (H) Made by Sumitomo Chemical Co., Ltd. 
Water Soluble Polymer (2)* 
##STR41## 
Surfactant (1)* 
Aerosol .RTM. OT 
Surfactant (2)* 
##STR42## 
Surfactant (3)* 
##STR43## 
Surfactant (4)* 
##STR44## 
Film Hardening Agent (1)* 
1,2-Bis(vinylsulfonylacetamido)ethane 
High Boiling Point Organic Solvent (1)* 
Tricyclohexyl phosphate 
Anti-fogging Agent (1)* 
##STR45## 
Anti-fogging Agent (1)* 
##STR46## 
Electron Donor (ED-11) 
##STR47## 
Reducing Agent (ED-37) 
##STR48## 
Electron Transfer Agent (X-22) 
##STR49## 
Sensitizing Dye (1) 
##STR50## 
Sensitizing Dye (2) 
##STR51## 
Sensitizing Dye (3) 
##STR52## 
Sensitizing Dye (4) 
##STR53## 
Yellow Dye Providing Substance (1) 
##STR54## 
Magenta Dye Providing Substance (2) 
##STR55## 
Cyan Dye Providing Substance (3) 
##STR56## 
The preparation of the emulsion (I) used in the first layer is described 
An aqueous solution (600 ml) containing sodium chloride and potassium 
bromide and an aqueous solution of silver nitrate obtained by dissolving 
0.59 mol of silver nitrate (in 600 ml of water) were added simultaneously 
at equal flow rates over a period of 40 minutes to an aqueous gelatin 
solution (containing 20 grams of gelatin and 3 grams of sodium chloride in 
1000 ml of water, maintained at a temperature of 75.degree. C.) which was 
being thoroughly agitated. Furthermore, 200 ml of a methanol solution of 
40 mg of the sensitizing dye (3) and 120 ml of the dye (4) were added over 
a period of 15 minutes from 30 minutes after the start of the addition of 
the aqueous silver nitrate solution. A monodisperse cubic silver 
chlorobromide emulsion (bromine content: 80 mol %) of average grain size 
0.35 .mu.m was obtained. 
After washing with water and removing the salts, 5 mg of sodium thiosulfate 
and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene were added and 
chemical sensitization was carried out at 60.degree. C. The recovery of 
emulsion was 600 grams. 
The preparation of emulsion (II) used in the third layer is described 
below. 
An aqueous solution (600 ml) containing sodium chloride and potassium 
bromide and an aqueous solution of silver nitrate (obtained by dissolving 
0.59 mol of silver nitrate in 600 ml of water) were added simultaneously 
at equal flow rates over a period of 40 minutes to an aqueous gelatin 
solution (containing 20 grams of gelatin and 4 grams of sodium chloride in 
1000 ml of water, maintained at a temperature of 75.degree. C.) which was 
being thoroughly agitated, and the dye solution (I), a solution, obtained 
by dissolving 160 mg of the sensitizing dye (D-22) in 400 ml of methanol, 
was added over a period of 2 minutes after the addition had been 
completed. A monodisperse cubic silver chlorobromide emulsion (bromine 
content 50 mol %) of average grain size 0.45 .mu.m on which the dye was 
adsorbed was obtained. 
After washing with water and removing the salts, 5 mg of sodium thiosulfate 
and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene were added and 
chemical sensitization was carried out at 60.degree. C. The recovery of 
emulsion was 600 grams. 
The preparation of emulsion (III) used in the fifth layer is described 
below. 
An aqueous solution (1000 ml) containing sodium iodide and potassium 
bromide and an aqueous solution of silver nitrate (obtained by dissolving 
1 mol of silver nitrate in 1000 ml of water) were added simultaneously 
while maintaining a constant pAg value to an aqueous gelatin solution (20 
grams of gelatin and ammonia dissolved in 1000 ml of water, maintained at 
a temperature of 50.degree. C.) which was being thoroughly agitated. A 
monodisperse octahedral silver iodobromide emulsion (iodine content 2 mol 
%) was obtained. 
After washing with water and removing the salts, 5 mg of chloroauric acid 
(tetrahydrate) and 2 mg of sodium thiosulfate were added and chemical 
sensitization with gold and sulfur was carried out at 60.degree. C. The 
recovery of emulsion was 1 kg. 
The preparation of the gelatin dispersion of the dye providing substances 
is described below. 
Thirteen grams of the yellow dye providing substance (1), 6.5 grams of the 
high boiling point organic solvent (1) and 6.5 grams of the electron donor 
(ED-11) were added to and dissolved in 37 ml of cyclohexanone and this was 
mixed with stirring with 100 grams of a 10% gelatin solution and 60 ml of 
a 2.5% aqueous solution of sodium dodecylbenzenesulfonate. The mixture was 
then dispersed in a homogenizer at 1000 rpm for a period of 10 minutes. 
The dispersion obtained is referred to as the dispersion of the yellow dye 
providing substance. 
The magenta dye providing substance (2) (16.8 grams), 8.4 grams of the high 
boiling point organic solvent (1) and 6.3 grams of the electron donor 
(ED-11) were added to and dissolved in 37 ml of cyclohexanone and this was 
mixed with stirring with 100 grams of a 10% gelatin solution and 60 ml of 
a 2.5% aqueous solution of sodium dodecylbenzenesulfonate, after which the 
mixture was dispersed in a homogenizer at 1000 rpm for a period of 10 
minutes. The dispersion obtained is referred to as the dispersion of the 
magenta dye providing substance. 
The cyan dye providing substance (3) (15.4 grams), 7.7 grams of the high 
boiling point organic solvent (1) and 6.0 grams of the electron donor 
(ED-11) were added to and dissolved in 37 ml of cyclohexanone and this was 
mixed with stirring with 100 grams of a 10% gelatin solution and 60 ml of 
a 2.5% aqueous solution of sodium dodecylbenzenesulfonate, after which the 
mixture was dispersed in a homogenizer at 1000 rpm for a period of 10 
minutes. The dispersion obtained is referred to as the dispersion of the 
cyan dye providing substance. 
The multi-layer color photosensitive materials described above were exposed 
for one tenth of a second using a tungsten lamp through B, G, R and gray 
color separating filters which varied the density continuously. 
The exposed photosensitive materials were fed at a line rate of 20 mm/sec, 
water was supplied with a wire bar at the rate of 15 ml/m.sup.2 to the 
emulsion surface and then the materials were immediately superimposed so 
that the film surface made contact with an image receiving material. 
The samples were then heated for 20 seconds using a heater roller of which 
the temperature was adjusted in such a way that the wet film temperature 
was 85.degree. C. On peeling away from the image receiving material, blue, 
green, red and gray images corresponding to the B, G, R and gray color 
separation filters were obtained on the image receiving materials (R-1) to 
(R-7). 
A transparent film which had an ultraviolet absorbing layer was 
superimposed on the film surface of these image receiving materials on 
which the images had been formed and the images were illuminated for 3 
weeks with the light from a fluorescent lamp (10,000 lux). The colored 
image densities were measured before and after exposure to the fluorescent 
lamp and the light fastness of the colored images was evaluated in this 
way. 
The maximum densities (reflection densities) and the dye survival rates at 
a reflection density of 1.0 were measured and the results obtained are 
shown in Table 3. 
TABLE 3 
______________________________________ 
Dye 
Image Maxi- Survival 
Expt. Colored Receiving mum Rate 
No. Image Material Compound 
Density 
(%) 
______________________________________ 
1 Yellow R-1 None 2.12 78 
Added 
2 " 2 II'-3 2.11 92 
3 " 3 II'-7 2.13 88 
4 " 4 II'-20 2.15 90 
5 " 5 V-2 2.12 93 
6 " 6 2-2 2.11 98 
7 " 7 III-6 2.09 93 
1 Magenta R-1 None 2.30 73 
Added 
2 " 2 II'-3 2.28 90 
3 " 3 II'-7 2.32 85 
4 " 4 II'-20 2.34 89 
5 " 5 V-2 2.33 90 
6 " 6 2-2 2.29 91 
7 " 7 III-6 2.34 92 
1 Cyan R-1 None 2.20 71 
Added 
2 " 2 II'-3 2.23 89 
3 " 3 II'-7 2.21 83 
4 " 4 II'-20 2.20 84 
5 " 5 V-2 2.19 88 
6 " 6 2-2 2.28 87 
7 " 7 III-6 2.24 89 
______________________________________ 
Dye Survival Rate =- 
##STR57## 
It is clear from the above results that the compounds of this invention ar 
effective. 
EXAMPLE 2 
The image receiving material R-8 was prepared by coating with the structure 
shown in Table 4. 
TABLE 4 
______________________________________ 
Structure of the Image Receiving Material R-5 
Amount 
Layer Number 
Materials Added (g/m.sup.2) 
______________________________________ 
Third Layer 
Gelatin 0.05 
Silicone oil (1)* 0.04 
Surfactant (1)* 0.001 
Surfactant (2)* 0.02 
Surfactant (3)* 0.10 
Matting agent (1)* 0.02 
Anti-stick agent (1)* 0.03 
Guanidine picolinate 0.45 
Water soluble polymer (1)* 
0.24 
UV absorbers (1)*-(3)* 
each 0.03 
Second Layer 
Mordant (1)* 2.35 
Water soluble polymer (1)* 
0.21 
Gelatin 1.40 
Water soluble polymer (2)* 
0.60 
High boiling point organic 
1.40 
solvent (1)* 
Antioxidant (1)* 1.00 
Compound (II'-21)* 0.40 
UV Absorbers (1)*-(3)* 
each 0.1 
Fluorescent brightener (1)* 
0.05 
Guanidine picolinate 1.80 
Surfactant (4)* 0.02 
First Layer 
Gelatin 0.45 
Surfactant (3)* 0.01 
Water soluble polymer (1)* 
0.04 
Film hardening agent (2)* 
0.30 
Support (1)* 
First Backing 
Gelatin 3.25 
Layer Film hardening agent (1)* 
0.25 
Second Backing 
Gelatin 0.44 
Layer Silicone oil (1)* 0.08 
Surfactant (4)* 0.05 
Matting agent (2)* 0.09 
Surfactant (5)* 0.01 
______________________________________ 
Anti-stick Agent (1)* 
Tetrafluoroethylene resin ("Teflon .RTM. 30-J" made 
by Du Pont-Mitsui Fluorochemicals Company, Ltd.) 
Ultraviolet Absorbers 
##STR58## 
##STR59## 
##STR60## 
Water Soluble Polymer (3)* 
Poly(sodium methacrylate) 
Antioxidant (1)* 
##STR61## 
Fluorescent Brightener (1)* 
##STR62## 
An image receiving material R-9 was then prepared in exactly the same way 
except that compound II'-21 in the image receiving material R-8 was 
replaced by compound A below of which k.sub.q .multidot.T.sub.1 had a 
value of 1.times.10.sup.4 M.sup.-1 .multidot.sec.sup.-1. 
##STR63## 
Blue, green, red and gray images corresponding to the color separation 
filters were then obtained on the image receiving materials R-8 and R-9 by 
using these image receiving materials with thermal development and 
transfer by following the same procedure as in Example 1, using the 
photosensitive material (K-1). 
The maximum densities (reflection densities) and the dye survival rates at 
a reflection density of 1.0 were measured in the same way as in Example 1 
and the results obtained were as shown in Table 5. 
TABLE 5 
______________________________________ 
Image Dye 
Colored Receiving Com- Maximum Survival 
Number Image Material pound Density Rate 
______________________________________ 
8 Yellow R-8 II'-21 
2.13 90 
9 " R-9 A 2.11 77 
8 Magenta R-8 II'-21 
2.32 89 
9 " R-9 A 2.29 77 
8 Cyan R-8 II'-21 
2.23 88 
9 " R-9 A 2.25 73 
______________________________________ 
EXAMPLE 3 
Photosensitive material K-2 was prepared in exactly the same way as 
described in Example 1 of JP-A-62-253159, and exposure and development 
processing was carried out in exactly the same way as described in Example 
1 of JP-A-62-253159 except that the image receiving materials R-1 to R-9 
of Examples 1 and 2 of this invention were used as image receiving 
materials. 
Image receiving materials R-2 to R-8 which contained compounds of this 
invention exhibited excellent fastness of the colored image when the 
yellow, magenta and cyan images so obtained were left to stand for 3 weeks 
under irradiation with the same fluorescent lamp as in Example 1 of the 
present invention. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.