Note: Descriptions are shown in the official language in which they were submitted.
SS~9
1 ~his invention relates to a ~olor diffusion
transfer process and a photographic element to be used
in the process. Particularly, the invention is concerned
with a color diffusion transfer process using a photo-
graphic element containing a novel color image forming
material.
; There are various color diffusion transfer
processes which are different in how color image fol~nlng
materials release di~fusible dyes during development of
silver halide, Among the prooesses~ a first typical
method, in which the so-called dye developing agent
being a compound having both a dye moiety and a silver
halide developing moiety in the molecule is employed as
a color forming material and oxidized with silver halide
to show a change in its diffusibility, is disclosed in
! various patents such as British Patent 804,971.
In a method using the above-mentioned dye
developing agent~ the dye developing agent which is
; sub~ected to diffuslon transfer to an image receivi~g
layer has a silver halide developing moiety and abounds
in reactivity. Therefore, resulting dye images often
suffer from color ~ontamination, a color tone change or
the like due to such reaction as air oxidation after the
diffusion transfer.
~ second typical method is such as using a
color image formin~ material releasing diffusible dyes f `
due to a coupling reaction or further due to a ring
closure reaction between a silver halide color developing
agent oxidized by silver halide and the color image
forming materialO
.' ~
S5~79~
1 This met~od for color diffusion transfer process
is disclosed in, for example, U.S. Patents 3,227,550,
3,443,941 and 3,227,551 and British Patent 904,365.
In the above-mentioned second method, i~ is
essential to use a silver halide color developing a~ent
as which ordinarily p-phenylenediamine type compounds
- are used.
The above-mentioned p-phenylenediamine type
compound~ in many cases give lmdesirable effects on dye
images because their oxidation products generally cause
color contamination. ~urther, the p-phenylenediamine
type compound~ have such defects as are apt to cause
dermatitis in the practical use thereof.
In addition to the above-mentioned ~irst and
second methods, there is a third typical method in which
employed is a nondiffusible color image fo~ming material
to be subjected to such reaction as an oxidation-
reduction reaction with an oxidation product of a silver
halide developing agent, and an oxidation reaction
directly with silver halide, thereby to release
diffusible dyes or their preoursors due to hydrolysis by
alkali or due to a ring closure reaction. This color
image forming material is called a dye releasing redox
comp~und whi~h will be hereafter ca~lled as a DRR compound.
This method for color diffusion transfer ~'
proce~s is disclosed 9 for ex~mple, in U.S Patents
3,698,897, 3,725,0629 3,728,113, 3,2~5,7899 3,443,9~9
and 3,705,035, U.S.B. 351,6739 ~rench Pa-tent 2,284,140,
Japanese ~aid-open-to-public Patent Publication Nos~
33,826/73, 118,723/75, 2,327/72, 104j343/76, 113,624/76
IL557~
1 and 64,436/74, Japanese Patent Publication No. 39,165/73,
Japanese Patent Application Nos, 78,057~76 and 125,357/76,
and Research Disclosures 15,157/76 and 15,654/77 ~
The above-mentioned third method is more
5 advantageous than the above-mentioned ~irs-t and second
methods in the respect that dye images of little color
cont~nination may be obtained because what is tr~lsferred
to an image receiving layer comprises a dye moiety or a
dye precursor moiety but does not comprise a silver halide
developing moiety and because it is not essential to
use a color developing agent such as p-phenylenediamine
type compounds and it is preferably possible to use a
black-and-white silver halide developing agent~
In the above-mentioned so-called DRR method,
a photographic element comprising a photosensitive
element having therein a light sensitive silver halide
emulsion layer and the so-oalled DRR compound associated
therewith is exposed to form latent images in sil~er ;
halide grains in the emulsion layer and then, processed
with an alkaline processing solution. The process~ng
may be conducted in -the presence of a silver halide
developing agent if desired. In the processing9 the ~`
above-mentioned photosensitive element and an image
receiving layer are superposed on each other so that
diffusible dyes or their precur~ors released from the
above-mentioned nondiffusible DRR compound are diffused
by transfer into the image receiving layer to obtain dye
images thereon, ~he DRR compounds suitable for this DRR
method have to meet such essenti~l requirements as
follows,
-- 4 --
~5S7~
1 (a) the compound should easily be dissolved into a
hydrophilic colloid,
~b) the transfer efficiency and the transfer speed o-f the
dye moiety or its precursor as transferred to the image
receiving layer should be high,
(c) the dyeability of the dye moie-ty or its precursor
transferred to the image receivin~ layer should ~e ~ood,
(d) the spectral absorption after the transfer should
give preferable color tone, and
(e) dye images formed in an image receiving layer should
sufficiently be stable.
~ urther, in case of using said DRR compound in
combination with a light sensitive silver halide emulsion
having spectral sensitivity substantially in the li~ht
absorbing region of the DRR co~pound, if the DRR
compound is contained in such layer as placed on the
exposure side of the light sensitive silver halide
emulsion layer or contained in the light sensitive
silver halide emulsion layer, the number of photons
absorbed by the silver halide is reduced due to the light
absorption by the DRR compound itself to ca.use the
desensitization. In order to a.void the desensitization, :~
there is developed the so-called shift type color
diffusion transfer process using such DRR compound as
temporarily shifted in its light-absorbing spectrum to
increase the quantum efficiency at the time of exposure
and returning irreversibly the temporarily shifted :`
light-absorbing spectrum to the non-shifted light-
absorbing spectrum at -the certain stage after the
exposure/ The shift type DRR compounds suitably used
15S7~
1 for the above-mentioned shift type color dif-fusion
transfer process have to meet the following essential
requirements (f) to ~h) in addition to the above-
mentioned requirements (a) to (e)o
(f) the compound should have an enough shi~t width ln the
light-absorbing spectrum not to impair the sensitivity
of the silver halide emulsion,
(g) the light-absorbing spectrum should irreversibly
return to the non-shifted light-absorbing spectrum
swiftly at the certain stage after the exposure, and
(h) it should not return to the non-shifted spectrum
before the exposure.
As those similar to the non-shifted DRR
compounds used in this invention, there is conventionally
known such DRR compound as having an azo dye moiety
having a dimethylamino group, an acetamido group or a
benzamido group. ~hese compo~mds, however, cannot be
said sufficiently to meet all the above-mentioned
requirements of (a) to (e~. For example, -the compounds
do not show a preferable color tone after the transfer
or dye images formed in an image receiving layer is not
sufficiently stable.
On the other hand, as a shift type DRR compound9
further, there is known such compounds as having an azo
dye moiety containing an acyloxy group therein ~his
shift type DRR compound, however, cannot satisfy all the
above-mentioned essential requirements of (a) to (h~ in
some way or other.
~mong the conventional shift type DRR compounds
there is not known such as similar to the shift type DRR
~5~i79
1 compounds used in this invention which compounds have an
azo dye moiety and an amino group substituted with ~n
aromatic group and an acyl group. Therefore, the object
of the present invention lies in providing a novel color
diffusion transfer photographic element and the process
therefor using a novel color image forming material and
particularly in providing a novel color diffusion
transfer process using a novel D~R compound. In other
words, the object of this inven-tion lies in providing a
novel color ~iffusion transfer photographic elemen-t and
the process therefor using a novel DRR compound meeting
satisfactorily all the above-mentioned requirements of
(a) to (e) which the DXR compounds should fulfil. i~ore
particularly, the object of this invention is in
providing a novel shift type color diffusion transfer
photographic element and the process therefor using a
novel shift type D~R compound which has as its
fundamental structure a novel DRR compound meeting
satisfactorily all the above-mentioned requirements of
(a) to (e) and which meets satisfactorily all the above-
mentioned requirements of (a) to (h).
-- 7 --
5i579
1 The other object of the invention lies in
obtaining stable dye images of clear a~d color tone by
using the above-mentioned color diffusion transer
process and elemen-t.
~he above-mentioned objects of this invention :
as well as the other objects which will be made clearer
later, may be accomplished by using a color diffusion
transfer process which comprises imagewise exposing a
photosensitive element comprising at least one light
sensitive silver halide emulsion layer and a nondiffusible
compound of the following general formula [I~ or ~II].
Formula [I~
[Ml~(Xl)q~Al~ll~ A2\[(X~)S-~ll]p
Formula ~II]
Z ~(X2)r-~3 N-A2-N=N-Al~ u
-N=N~Al~ ( Xl ) q~ 2 \~ ( x )
A2-N=N-Al . "
A3- / ;
[In the above formulaeo A1 represents an aromatic
hydrocarbon group which includes substituted aromatic
hydrocarbon, an aromatic heterocyclic group which
includes a substituted heterocyclic ring, a nonaromatic
heterocyclic active methylene containing group which
includes a ~ubst.i.tuted nonaromatic heterocyclic active
5579
1 methylene containing ring, nonaromatic heterocyclic
active methine-con-taining group which includes a
substituted heterocyclic active methine-containing ring,
an aliphatic active methylene~containing group which
includes the substituted,
an aliphatic active methine-containing group which
includes the substituted,
or a group of the formula -A4-N=N-A5- (A4 an~ As each
represent here aromatic hydrocarbon group, an aromatic
heterocyclic group, a nonaromatic heterocyclic active
methylene-co~taining group, a nonaromatic heterocyclic
active methine-containing group, an aliphatic active
methylene containing group or an aliphatic active
methine-containing group all of which groups include
the substituted as mentioned above) 9 A2 ~nd A3 each
represent an aromatic hydrocarbon group or an aromatic
heterocyclic group both of which include the
substituted9 Ml represents a dye releasable monovalant
moie-ty9 M2 represents a dye releasable divalent moiety;
Xl, X2 and X3 each represent a divalent joint group9
Z represents hydrogen or a group of the formula YC0- in
which YC0 represents a hydrolyzable group9 m, n and p
each represent zero or a positive inte~er and the
combined number of m~ n and p is not less than 19 q, r
and s each represent zero or 19 and t 9 u and v each
represent 0, 1 or 2 and the combined number of t, u and
v is 2~,
developing the photosensitive element with an alkaline
processing solution in the presence of a silver halide
developing agent, releasing a diffusible dye from -the
31 l~SS79
1 said compound and carrying out the di-f~usion transfer of
the diffusible dye to an image receiving layer
corresponding to the imagewise exposure.
Further detailed description will be made below
as to the compounds of the above-mentioned general
formula ~I~ or ~II]
As to Al, A4 and A5 in the above formula,
the aromatic hydrocarbon group includes a benzene group~
a naphthalene group, a phenol group, a naphthol groupg
an anilino group, a naphthylamine group9 a diphenylamine
group, a monoalkylamine group and a dialkylaniline group.
As the aromatic heterocyclic group, there may be
included a pyridine group, a pyrimidine group, a furan
group, a thiophene group, a pyrazolone group, a
pyrazolobenzimidazole group, a pyrimidazolone group,
a 2,4-dihydroxyquinoline group, a methylindole group,
an N-ethyloxyindole group, an ~-phenyl-~-anilinoglutacon-
imide group, a thioindo~yl group, a cowmaran-3-one group
and a l-acyl-3-oxoindoline group. As the nonaromatic
heterocyclic or aliphatic, active methylene- or methine-
containing group, there may be included a 3-phenylisoxa-
zole-5-one group, a 2,4-dioxochroman group, a 1,3-
indanedione group, a 1,3~cyclohexanedione group, a
benzoylacetanilide group, a 2-(2'-cyanoaoetyl)-coumarone
group, a pivaloylacetanilide group, a p-nitrophenyl
acetic ester group and an ~-cyanoacetophenone group.
The aromatic hydrocarbon groups, aromatic
heterocyclic groups and nonaromatic or aliphatic active
methylene- or methine~containing groups include those
substituted further with other substltuents. As these
S~
1 substituents, there may be various groups such as alkyl
groups, aromatic hydrocarbon groups, alkyloxy groups,
aryloxy groups, halogen, .nitro, cyano 9 amino,. acylamino
groups, alkylamino groups~ arylamino groups, aeyl groups,
ac~loxy groups 9 aralkyl groups 9 hyarOxyl9 carbamoyl
groups, alkylcarbamoyl groups, arylcarbamoyl groups,
sulfamoyl groups, alkylsulfamoyl groups9 arylsulfamoyl
groups, amido groups, sulfonamido groups, carboxyl,
sulfo~ halogen-substituted alkyls 9 alkylsulfonyl groups,
arylsulfonyl groups, carboxylate groups, alkylearbonyl
groups and arylearbonyl groups and combi.nation groups
of the above-mentioned groups.
Among the groups as represented by A1, suoh
groups as an aromatic hydrocarbon group and an aromatie
heterccyclic group are preferred in this invention and
those which show the most preferable effect in the
process of this invention are such group as a benzene
group or a naphthalene group. A is an (m-~l)-valent
group in formula ~I~ 9 a divalent group in the brackets
having an appendix t in formula ~II), and a monovalent
group in the brackets having an appendix u or v in
formula ~ or example, therefore, ~hen A is mono-
valent, the benzene group is a phenyl group while the
naphthalene group is a naphthyl group. When A is divalent~
the benzene group is a phenylene group ~hile the n~phthalene
group is a naphthylene group.
With respect to A2 and A3 in formulas ~I~ and
~ , the aromatic hydrocarbon group include~s a benzene
group and a naphthalene group as in the case of Al. As
~0 the aromatic heterocyclic group, the-re m~y be included
.. .
5~79
1 a pyridine group, a pyrimidine group, a furan ~roup, a
thiophene group, a pyrazolone group, a pyrazolobenzimida~ole
group, a pyrimidazolone group, a quinoline group and an
indole group. ~hese aroma-tic hydrocarbon groups or
aromatic heteroc~clic groups include those substi-tuted
with one or more of various groups The substituents
showing preferable effects in this invention may include
alkyl groups, aromatic hydrocarbon groups, alkyloxy
groups, aryloxy groups, halogen, nitro7 cyano, amino9
acylamino groups, alkylamino groups1 arylamino groups 9
acyl groups, acyloxy groups, aralkyl groups, hydroxyl,
carbamoyl groups, alkylcarbamoyl groups, arylcarbamoyl
groups, sulfamoyl groups, alkylsulfamoyl groups,
arylsulfamoyl groups, amido groups, sulfonamide groups,
carboxyl groupS,sulfo, halogen-substituted alkyl groups,
alkylsulfonyl groups, arylsulfonyl groups, carboxylate
groups, alkylcarbonyl groups and arylcarbonyl groups
and combination groups of these groupsO
A2 is (p+2) valent in formula ~I~ while A2 is
divalent in the bracket having a~ appendix t or u in
formula LII~ Moreover, A2 is tri-valent in the brackets
having an appendix v in formula ~ O On the other hand,
A3 is (n~ valent in formula [I~ while A3 is monov~lent
in the brackets having an appendix t or v in formula
In addition, A3 is divalent in the brackets having an
appendix u in formula LII].
Among the above-men+ioned groups represented
by A2 and A3, -those having particularly preferable
effects in carrying out the process of the present
invention are aromatic hydrocarbon groups.
_ 12 -
SS7S~
1 Further, the group of the for~ula -N-A~ is
directly bonded at the proper position on the nucleus
which -~orms an aromatic ring of the aromatic groups for
A2, and preferably bonded at the position adjacent to a
position to which the -N=N- is attached.
Ml represents a dye releasable monovalent moiety
which is the so-called carrier moiety which releases
diffusihle dyes from the compound of the above-mentioned
formula tI~ as a function of oxidation under alkaline
conditions, particularly at a hydroxidion concentration
of 10-5 to 2 mole/l.
As a typical example of the Ml moiety of the
D~R compound of the general formula ~I~ used preferably
in this invention, there may be included those having
the following general formula ~III] to rXII~Jo
General Formula
Q ~
~IHS02- ~'
In the above formulao Q represents a nonmetallic
atom grouping necessdry to form a 6-membered aromatic ring,
which includes a fused ring, preferably such as a benzene
ring or a 10-membered aromatic ring preferably like a
naphthalene ring and a quinoline ring. The 6-membered
aromatic ring includes those substituted with such as
halogen, a lower alkyl ~roup or a lower alkyloxy group;
represents an organic ballast group making immovable
- 13 -
, . ~
,
` l~lSS7~
l and nondiffusible the compound o-f the general formula rI~
having the group of the general formula [IIIJ as Ml~
under the alkaline conditions preferably at the hydroxidion
concentration of lO 5 to 2 mole/l, As the organic
ballast group, there may be included long chain alkyl
groups, aromatic groups such as benzene type or naphthalene
type, or long chain alkyl groups or aromatic groups
which are bonded with one end of suita~le divalent groups
` such as the group represented by -Xl- in the above
general formula rI~ or [II~ and which -Xl- will be ,
described below more particularly. As the pre~erable
examples of the organic ballast group represented by B
in the compound of the general formula ~I~ relating to
this invention, there may be included substituted or
unsubstituted C8-22 alkyl groups. Similarly, there may
be included the alkyl groups which include~ those
substituted with a C8-22 alkyloxy group or the like at
the terminal end o-f a divalent group comprising any
1l
combination of such groups -C-, -N-, -CH2-, phenylene
group, -0- and -S02- and the groups ~hich are bonded with
a phenyl group or a naphthyl group including those
substituted with an alkyl group, an alkyloxy group or
the like.
D represents -ORl or -NHR2. Herein R
represents hydrogen or a hydrolyzable group which cleaves
the linkage between Rl and 0 pre-ferably under a hydroxidion
concentration of lO 5 to 2 mole/l and pre-ferably represents
O O -
Il 11
hydrogen or a group of the formula -CR3 or -C-0-R3
~5~
1 Herein, R3 represents an alkyl group, particularly a Cl-18
alkyl group Like a methyl, ethyl or propyl group, a
halogen-substi-tuted C1-18 alkyl group like a chloromethyl
or tri-~luoromethyl group, or a substituted or unsubstituted
phenyl group. And R2 represents hydro~en, a Cl-22 alkyl
group or a hydrolyzable group which cleaves -the linkag~e
between R2 and N preferably under a hydroxidion
concentration of 10-5 to 2 mole/l, The preferable
hydrolyzable groups are those having a group of the
formula -CR4, -S02R5 or -SOR5. Herein R4 represents a
Cl-4 alkyl group like a methyl group, a halogen-substituted
alkyl group like a mono-, di- or tri-chloromethyl or
trifluoromethyl group, an alkylcarbonyl group like an
acetyl group, an alkyloxy group, a substituted phenyl
group like a nitrophenyl or cyanophenyl group, a phenyloxy
group including those substituted with a lower alkyl
group or halogen 9 a carboxyl group, an alkyloxycarbonyl
group, an aryloxycarbonyl group, an alkylsulfonyle-thoxy
group or an arylsulfonylethoxy group. R5 represents a
substituted or unsubstituted alkyl or aryl group.
~urther, X is 0, 1 or 2, preferably 1 or 2.
Except for the case that R2 is along chain alkyl group
such as a ~ ~ C22 alkyl group in the formula -NHR2
into D, X is 1 or 2, preferably 1. ~ ;
~he preferable examples of the M1 moiety of the
above general formula ~III] in this invention may be as
followsO
- 15
lS~;7
1] OH
) 3lcl5~
NHSO2
[III-2~ '~H2
~b
(n)H31C15/~ . .. ..
NHSO2- :
LIII 3J I 12~25(n)
NHSO2-
[III-4~ HNC2H5
d~ ,
( )C8H17/~ '`
NHS02-
~III-5] 4 9 (
( n )H ~jl C15 : ~
~s2
~III-6] OH C5H11(t)
~Co~(C~2),50~C5~11(t)
H3C
NHSO2-
~III-7] HNC12H25(n)
NHS02
-- 16 - ~
11557g
8] OH
NHC18H37(n)
N~SO2
[III-9~ OH
CONH~
~ OC14H29(n)
[III-10] OH C5~t )
~ CON~I(CH2)40~ C5Hll(t)
NHS02- ~ ~,
HNC12H25 ( n )
NHS02 ~' '
`rIII-12] HNS2C16H33(n)
~ OC2H5
H5C20 1 ~,
~SO2-
13] HNCO~
~"~OC2~5
H5C2 T
.; . . . ~ .
-- 1 7 -- . .
1 General ~ormula [I~
ORl
Q ~ L-
(B)
ORl :
In the above formula, B, Rl~ Q and x
are as explained before and ~ represen~s -SO2-, -S- or -O-,
~he preferable examples of the ~l moiety having
the general formula [IV~ in this inven-tion may be as
follows~
rIV-l] OH
~ Cl
( ) 31 15 ~ S2-
OX ::~
~IV-2~ OH
~ "
( ) 31 15~ SQ2
OH
~IV-3~ OH
(n)~133C16~3/ 2 ;
OH
.
~ - 18 ~
5S7~
rIV-4] OX
Cl~ O-
( ) 15 31 ~\Cl
OH
rIV-s ] OH
Cl~ Cl
(n)C15~31~\ O-
OH ,
rIV-6]OH
~Cl ~:
(n)C 5~ ~o_ ~ -
0~ ~;
[IV-7 ]o~
Cl~O-
(n)C18H37/~Cl
OH
[IV-8~OH
(n)C H ~l ~O-
Cl/~\Cl
OH
[IV-9]OH `: " ""
(n)C8H17~0-
Cl 8 17( )
OH
- 19 - ~ ;
~ ;5~
[IV~10] OH
(n)
~ O- .
OX ~ : :
[IV. 11~ OE
(n) 15H31\~
~0- . "'
OX
1 General Formula ~V~
OH
R6 \~ C~2-G- ,
R
Rg
In the above formula. R6 represents hydrogen,
an amino group, an alkyl group or an aryl group; R7 and ~ ;~
Rg each represent hydrogen, an alkyl group or an aryl
group; R8 r~presents hydrogen, hydroxyl9 an alkyl group
or an aryl group but, when R6 is a hydrogen atom, an
alkyl group or an aryl group, R8 is hydroxyl 9 and G
represents the group of the formula
IR 10
~ An~, S ~ An~, S' or NSO2 (herein, L~lG and R'10 each
10 '
represent an alkyl group or an aryl group, and Rlo and
R'lo, together with a ~ atom, may form a divalent
pyridinium group or a divalent piperazine group, and An~
represents an acidic anion)~
-- ~0 --
1~5S79
1 It is preferable that one or two members ~mong
R6, R7, R8 and Rg are a group represented by B in the
above-mentioned general formula ~III]~
~he examples of the Ml moie-ty ha~ing the above
general formula [~ may be as followso
~V-l] OH I 3
2 1
OH B~3
rV-2] OH f 3
C8H17~ C~2-1$3;
OH Br~)
[V-3~ OH I 3
CH3 fH3 ~CH2 Nq~)
CH3-C-cH2-c ~ 3 `;
CH3 CH3 OH C1~3
,
~V-4] OH CH
, ~a~2-~0-
OH B~
[V-5] OH
~ C~2~
( ) 18 37
O~ Cl~
- 21 -
55~7~
~V-6~ OH
f~r CH2-~N~,
( ) 14 29 Cl(3
OH
~V-7~ OH ,
~1 CH2 ~N~
(n)C12H25/~ Cl(3
OH
[V~]f ~ f 3 CH -~N~
CH3-CI-CH2-Cl ~ ;
C~3 CH3 OH Cl~
[V-9] OH
~"~CH2~
) 10 21 OH Cl(3
~V-10] OH I 3
1 3 f 3 f~--CH ~N N-
CH3-C~CH2-C~, 1l 2 ,
CH3 CH3 OH C10
General ~ormula ~VI~
D~
( B )~
~q Rll
'
- 22 -
-" 311~5iS~7~
1 In the above formula, B and B', Q and Q', and
x and x' are as explained be:Eore; ~' represents
-C- or -SO2- 9 Rll represents hydrogen or an alkyl group~ .
D' r0presen~Gs hydrogen, hydroxyl, an acyloxy group or ;~
the group of the formula ~< 129 and D" represents
R13 R12
hydroxyl, an acyloxy or the group of the formula N <
(wherein, R12 and R13 each represent hydrogen, an acyl
group or a hydrocarbon group).
The examples of the Ml moiety having the above
general formula ~VI~ may be as follows~
[VI-l~ O
-N--S-
NH H O
25C12~ C ~ ~ CH3
~VI-2~ OH o H
12 25
~ O ~:~
-N-S
H o
- 23 -
5S~7~
~VI-3]CH
~ .
NH O
¢ ~ Dll~l `:
O
12H25 CH3 :
[VI-4~ OH O
H7C ~ CH2CH2-C-N~l-Cl2H25
H ~;C/~
NH O
DIHS_
O ~ ~.
[VI-5 ] OH
CH30-¢~CH2CH2CNHC12H25
NH O
~NHC-
~VI-6~ OH
COOH
NH
--NH-S02-
~ , ;.
NH
C=O
2 16 3
-- 24 --
~L~15~79
, ~ :
' ~
~VI-7 ] OH
1~ . :
f~ NH~2
NH
C=O . ,' '
(1H2 )16CH3
[VI~1 H I H
~CH2-CH2-c-M-(d~2)ll 3
~H
~HSO2- .
[~-9~ OH O H
CH2-CH2-C-~-(CH2317 3
~NE~2- ~
General Formula ~JII] ~ -
"R14 :~ '
B )x ~ C=N-NH- ( L ' )y~
Rl 5
- 25
5S7~9
1 In the above formulao R14 represents hydrogen,
an alkyl group, an aralkyl group or an amino groups and
R15 represents an alkyl group, an aralkyl group, an aryl
group, an acyl group or an amino group, and R14 and R~5
may be bonded with each other to form a hydrocarbon ring
or a heterocyclic ring9 ~' represents a group of the
O
formula -C- or -SO2-9 y is zero or 19 and, B and x ~re
as explained before.
r~he examples of the Ml moiety having the above
general formula ~VII] may be as follows.
[VII-1] ~02 ~ ~=C )~ 16
( IH2)3
so ~ .
LVII-2] S
-S02-I7H--N=C )~ 12X25
N
(fH2)3
LVII 3] D~
~02-~X-N=CH ~ C16~33
~VII-4] -SO2~ -N=CH~
33
-- 26
~1~5579
[VII-51 S
-S02~ N=C~ ~ 3
C16~33
~VII-6~
S02-NH-N=f--6~ C12H25
CH3 : ``
[VII-7
-S02-NH-N=f -C17H35
[VII-8
-S02-NH-N=CH-C6H13
~VII-9] . S
-SO -~X-~ ~q
~N/~S03H
C16H3
~VII-10]
N
f=N-NH-S02-
¦¦ H ~ ~;
C~H2 C N~
fH-C16H31 ~ ,.
C=O , ,
OH
7 -:
.
SS7~ ,
~VII 11~ C117H35
-S02~ N~
(1~2)3
So~H
General Formula LVIII]
) y~ lCI -MH-I~I-S 02-B
w
General Formula [IX~
B-(~ )y~C~NH~NH~S02~
W
1 In the above two formulaeO B is as explained
before; ~"'represents a group of the formula -O-, -S-,
' 2 , CONR16- or -S02NR16- (In the ~ormulae 9
R16 represents hydrogen or an alkyl group.); W representg
oxygen, sulfur or an imino group; and y is zero or 1.
- The examples of the Ml moiety in the above
formulae ~VIII~ and [IX] may be as follows
rVIII-l]
ON~ H-S02 C17H35(n)
~VIII-2~ -CON~NX-S02~ 15 31 (
~IX-l~
2 ~H-NX-CO-C15X31 (n)
- 28 -
- ~lS~i7~
~IY~-2]
[IX-~ ~02-NH-NECO-O-Cl8H37(n)
~IX-4] ~2 ~E-NH-11-al,~35(n)
NH
l General Formula
Z'-C-~H-NH~O -B
~(~"')y~ ¦¦ 2
General Formula [XI]
Z~-C-NH-NH~02-
B-(L"')
In the above two formulaeo B, ~"'and y
; are as explained before9 and, Zl represents a nonmetallic
atom group necessary to form together with a carbon atom
or a nitrogen atom a 5- or 6-membered, non-condensed
or condensed heterocyclic ringO
The examples o-f the Ml moiety having the above ~:
general for~lulae ~X~ and ~XI~ may be as followso
1',
LXI-1] ~ -
(n)C12H25-EN ~
N ~-- NENH~O -
H03S-CH2CH2-~H
~ -- 29 - ~
SS7
~XI_2~ N
3SC~2C~2~HCO~ ~NHNH~O2-
~ N NHC12 25(n)
LXI-3~ (n)C12H25NX~O2 ¢~ /~NHNH~O2
1 General ~ormula ~XII]
,~ Q "~
B - C=D"'
~ Rl8
NIIS02-
In the above formula, B is as defined before.
D"'is oxygen or a group of the formula =NR17
(where, R17 represents hydroxyl or an amino group which
includes the substituted) and, particularly when
D"'is -NR17, the representative R~7 is chose in the
group of the ~ormula~C=N-R17 which is formed by
carrying out the dehydr~tion reaction of the carbonyl
reagent H2~-R17 with a keton-containing group.
As this H2N-R17 compound, there may be included, for
example, hydroxylamines, hydrazines, semicarbazides
and thiosemicarbazides. More particularly, the
hydrazines may include hydrazine, phenylhydrazi~e 7
subs-tituted phenyl hydrazine having on its phenyl group
a substituent such as an aryl group9 an alkoxy group, a
carboalkoxy group or halogen, and isonicotinic acid
- 30 -
S57~ ~
1 hydrazine. ~nd the semicarbazides may include phenyl-
semicarbazide and substituted phenyl semiearbazide
having on the phenyl group a substituent such as an
alkyl group, an alko~ group~ a ca~bo~lkoxy group or
halogen and the thiosemicarbazides may also include
various derivatives thereof as the semicarbazide.
Q" in the formula ls a saturated or unsaturated
5-, 6 or 7-membered nonaromatic hydrocarbon ring and
may inelude as its typical example, for example, cyclo-
pentanone, cyclohexanone 9 cyclohexenone, cyclopentanone,cycloheptanone and cycloheptenone.
~ urther9 these 5-7 membered nonaromatic
hydrocarbon rings includes a condensed ring fused
with another ring at their suitable positions.
15 This partner ring -~or condensation may include ;
various rings, whether they have aromaticity or not
or whichever they are hydrocarbon rings or heterocyclic
rings, but in this invention more pre-ferable is a
ring formed by fusing the above-mentioned 5-7 membered
nonaromatic hydrocarbon ring with benzene such as
indanone, benzocyclohexenone or benzocycloheptenone.
~ he above-mentioned 5 to 7-membered nonaromatic
hydrocarbon ring or the above-mentioned condensed ring
may be having one or more substituents such as an alkyl
group, an aryl group, an alkyloxy group, an aryloxy
group, an alkylcarbonyl group, an arylcarbonyl group,
an alkylsulfo1lyl group, an arylsulfonyl group, halo~en,
nitro9 amino, an alkylamino group, an arylamino group,
an amido group, an alkylamido group, an arylamido group,
- 31 -
7~
1 cyano, an alkylmercapto group or an alkyloxycarbonyl
group.
Rl~ represents hydrogen or halogen like
fluorine9 chlorine or bromine.
The examples of the Ml moiety having the
above general formula ~II] may be as follows~
rXII~
(t)C5H
NHCOCH20 ~ (t)C5H
2-
~XII-2~
(n)C12~25~0~rl01~02~
[XII-3
(n)C16~3~~2 ~ ~2
. O
. . .
~ - 32 -
SS'7~
~XII-4]
(n)C12H25-NHS2~ H ¦
~\NHS0
O
~XII-5 ~
(n)CI2H25CONH~ W NHS02
O ~,"
[XII~6~
~1 ' ' '.~
(n)ClOH21~/\~HS0
O
1 General Formula [XII'~
OR
~ S2-
G~
Gm-l
: ~.
In the above formula, G represents an aroma-tic
ring directly fused to the benæene nucleus to form a
naphthalene nucleus9 m and n each are 1 or 2 and different
from each other9 Rl and ~ each are defined before.
~ he examples of the ~ moiety having the above
general formula ~XII'~ may be as followsO
- 33 -
lSS~
2 NHS02
OE ~¢~ OH
C-NH(CH2)40~3 C H -t
CrHll t
C14H29 n
rl~ls2- NHS2
OH ~\~
C18H37-n
S02NH( CH2 )4-O~ C5Hll-t
C5Hll- t . ,~
NH$02~ 02
18 37 ~ OH
So2NHCH2CII-o~3 5 11
C5Hll-t
NHS02 N~S2~
~¢~5C18H37-n ~li `;r OH
So2NH~
~ISO2- C14H29 n
D\,~o~
~,i~/l S02Cl~H37-n NH~16H33-n
~¢~IIH802 1~" ~CH
S2N'(C12H25-n)^
-- 34 --
. .
~L55'?'9
1 General Formula CXII"] :
ORl
Xn $~ ~2
OR
In the above-formula, R represents an a.lkyl
group or an aromatic hydrocarbon group9 Rl is as defined
before; X is a monovalent group or an atomic group to
5 form, together with the -OR group, a condensed ring fused : ~:
to the benæene nucleus, the ring not being an aroma~ic
hydrocarbon ring9 and n is 1, 2 or 3, provided that the
combined carbon number of Xn and R is not less than 8,
further provided that a ~lurality o-f Xs if present may
be different, and still further provided that X is an
electron-donor group when n is 1 while at leas-t one of a
plurality of Xs is an electron-donOr group when n is 2
or 3.
'~ypical examples for the -OR group is an acyloxy
group such as a propionyloxy group and an acetoxyl group
in addilion to hydroxyl~ ;
The examples of the M1 moie-ty having the above
; general formula ~XII"] may be as followso ~`
. '.
OH O~
~HSO2 ,~NHSO2~ :
CH3
C16H33 C18E37
. ~ OE OH ;-~
~C31'6!'1~ C15~
~ 35 ~
.
55~7g
o~ o~ . ;.
,,~N~IS02- ClX~ ~o~-
C~I3 3
C16H33 Oal8~I37
OH So2-
~H3 ~ ~02- N~ CH3
C~[3~(C~2C~2C~27~t3C~3 ~' .11~ ~
CH~ CH3 OH ¦ 3 1 3
CH3-C-CH2-f ~ ~ 2- CH3-7-CH2-C ~ ~2-
3 3 C6Hl3 CH3 CH3 0 ~ 3
. CH3 CH~
:,
1 In the above-mentioned for~ula [II~, ~s
defined before M2 is a divalent dye releasable moiety
which is the so-called carrier moiety which releases ;~
diffusible dyes from the compound of the general ::
formula ~ as a function of oxidation under alkaline
conditions9 preferably at a hydroxidion concentration :
of 10-5 to 2 mole/l.
The M2 moiety of the compound of the above
general formula ~ used advantageously in this
invention may include such as having the following
general formula ~XIII~o
- 36 -
~SS'7~
1 General ~`or~ula ~XIII]~
-~o2~ Ar-~H-so2-
In the above formula Ar represents an
aromatic hydrocarbon group which includes those
substituted with an alkyl group9 halo~en or an alkyloxy
group, particularly preferably with an alkyloxy group,
provided that the two l~H groups are connected through
1-4 combinations of the two carbon atoms in the aromatic
hydrocarbon group.
The examples of the M2 moiety having the
general formu a [XIII~ may include as follows: ~
, ,
[XIII-l] ~ NHS02
[XIII-2~ -S2~H ~ ~ - ~ISO -
[XIII-3
~02NH~ N~IS02
- ~7 - .
IL5579
rXIII--4~ 2 5 ~ :
~2~2- ,`
C2H50
~XIII-5] C4Hg~n)
-S02NH~ NHS02-
(n)C4HgO
[XIII-6~ 12H25(~) :
~02-~2~
(n)~12H25
~XIII-7~
~o2NH~02'' :~
1While the Ml and M2 moietles are explained
above in detail, the most preferable effect may be
obtained in this invention in the case that the Ml
moiety in the compound of the general formula ~I~ has ~ :
formula ~III~.
In the above general formulae ~I~ and ~ 9
Xl, X2 and X3 each represent a d~valent joint group.
The preferable Xl, X2 and X3 in this invention are a
divalent joint group being one member selected from,
or any linear combination of two or more members
belonging to7 the group consisting of -O-, -$-,
~5S~
O 1 19
2-~ -S0-, -N-, -~R20R2~ CR20=~l'21
above formul.ae, R19 represents hydrogen, an alkyl group
or an aromatic hydrocarbon group! and R20 and R2l each
represent hydrogen, halogen, an alkyl group or an
aromatic hydrocarbon group), substituted or unsubstituted
aromatic divalent groups aMd the groups of the following
formulae- :
(X' ) /(X )a\R20 R~,(X )a\R20
\X"/ \X"/ aMd ~C\X''/C~ "
(In these above three formulae~ X' and ~" each represen-t
a divalent group being one member selected from, or
any combination of 2 4 members belonging to, the group
Il .
consisting of -0-, -~ C-, -S02-, -S0- aMd the above-
llgmentioned groups of the following formulae -N-, -CR20R~l-
and -~R20=aR2l~; a is zero or 19 and, (X')a and X"
-together with N and/or C ~orm as a whole a 5 or 6-
membered ring.)
Further, the more preferable case in this
invention i9 when Xl, X2 and X3 are the groups of the ~ :
formula -
R22 R22
El~Jl)b (~2)c ~( N )d J2t N
In this ~ormulao El and E2 each represent, a C1-8 alkylene
group or a phenyl_ne group and these alkylene aMd
phenylene groups include those substituted with halogen, .:
an alkyl group or an aromatic hydrocarbon group 9 R2z and
_ ~9 _
5~i79
1 R22' each represent hydrogen, a Cl-8 alkyl group or a
~6-1~ aromatic hydrocarbon group such as a phenylene
group, a tolylene group or a naphthylene groupy
O O O O
Il 11 11 11 ;
Jl represents -0-, -S-9 -C ~ -C 0-9 -0~ -OC-O-~
O O
~ H ~ H
-NC-, CN-, -NS~2-, -S02N-, -S0-, -S02-, a al-8 alkylene
group including alkylene substituted with halogen, or an
unsubstituted or substituted phenylene groupp J2
O :.
represents -S02- or -C-9 b and c each are zero or 1 but~
when b is 1, c is 1 and, when b is zero, c is zero or 1
(provided, when c is 1, the total C number of Bl and ~2
is less than 15)9 and~ d, e and f each are zero or 1 and
the total of d and e is 1.
In the above general formulaa ~I~ and
the YC0-group for Z represents a group hydroly~able .
preferably at a hydroxidion concentration of 10 5 to
2 mole/l in order to be cleaved off -from the bonding
with the nitro~en and in this case the compound of the
: general formula [I~ or ~ is the so-called shift type : :
DRR compoundO As the Y in the g~oup YC0 having a
preferable effect in this invention, there may be
included C1~5 alkyl groups such as a methyl group7 ~n.
ethyl group9 a propyl group9 an isopropyl. group9 C1~5
alkyl substituted with halogen a-t the ~ or ~-position
such as chloromethyl, dichloromethyl, trichloromethyl,
bromomethyl, dibromomethyl, tribromometh~l9 tri~luoro-
methyl, ~-bromoethyl, ~-bromobutyl, pen-tafluoroethyl and
- d bromoisopropyl9 C1-5 alkyl substi-tuted at the ~ or ~-
~.
-- ~0 --
lgL~LS5'7~39
1 position with a substituted or unsuhstituted aryloxy
group or a substituted or unsubstituted al-5 alkyloxy
group such as methoxymethyl, propoxymethyl, phenoxymethyl
and ~-phenoxyethyl9 Cl~-5 alkyl substituted at the ~- or ~-
position with hydroxyl such as hydroxymethyl, As suchthe Y, there may further be included a vinyl group
substituted with substituted or unsubstituted Cl-5 alkyl
groups or aryl groups such as ~methylvinyl and ~-
phenylvinyl; aryl groups having 1-3 substituents such
as halogen, nitro, cyano and trifluoromethyl9 or the
group of the formula -OR23 or -C-OR24 (in which R23
represents a substituted or unsubstituted, Cl-5 alkyl
or phenyl group9 and, R24 represents such group as
represented by R23 or hydrogen. As the substituent in
the alkyl groups, Cl-5 alkylsulfonyl groups? amido
groups, hydroxy, carboxyl, alkoxy groups and h(~logen
are preferabls. And as the substituent in -the phenyl
groups, halogen, nitro, cyano, -trifluoromethyl and
20 methyl are preferable and it is preferab]e that 1-3 -
substituents are presented in the phenyl group.) The
examples for -OR23 are ethoxy ~-methylsulfonylethoxy9
phenyloxy, ~-chlorophenyloxy. The examples for `
-~-OR24 are ethoxycarbonyl and carboxylO
~he more preferable in this invention among
the groups for Y in the formula YC0-, are Cl-5 alkyl
substituted, at the d- or ~-position, with halogen or a
I l . ~
group of -the formula -OR23 or a-Q-R24, the most
preferable being trifluoromethyl.
- 41 -
S~;79
1 With respect to m, n and p in the before- :
mentioned formula ~I], it is more preferable that m, n
and p each are zero or l and the total of m, n and p is
l. It is still more preferable either that n and p each
are zero and m is 1 or that m and p each are zero and
n is l. In addition to this case, when the groups
represented by Al, A2 and A3 are aromatic hydrocarbon
groups, the best effect may be shown in this invention~
As to t, u and v in the above-mentioned general
formula ~ , the best effec-t may be shown when t is 2.
In ~he above-mentioned formulae ~I~ and
q, r and s each are zero or 1.
Among the compounds of the general formula ~I~
or ~ as specified in detail? those showing much more
preferable effects in this invention are compounds of
ths following general formula ~XIV]~
General Formula ~XIV~
R(l) R(2)
~Ml~(Xl)q ~ Al ~ R(3)
R(4) (R(5))
In the above formula, Al' represents a
substituted or unsubstituted 9 aromatic hydrocarbon or
20 aromatic heterocyclic group. As the substituent on the~ :
aromatic hydrocarbon or the aroma-tic hetero ring, there
may be included those described above as the substituents :~
of A2 or A~ in the above general forrnula ~I~. Ml r ~1~ q
; and m each are as defined beforeO R(l), R(2) and R(5)
each represen-t hydrogen9 halogen? nitro 9 an alkyl group
- ~2 -
.. . .
5S~9
1 including halogen-substituted alkyl (for example,
trifluoromethyl and chloromethyl), hydrox~yl, a group of
the form~a -OCOY' (herein, the Y' ao- in the -OCOY' group
represents a hydrolyzable group which cleaves the bondage
with an oxygen atom preferably at a hydroxidion
concentratio~ of 10 5 to 2 mole/l. The group of ~'C0-
having more preferable effects is the group o~ the
O O
~ormula R(6) -C- or R(6)-0-C-. In these cases, R(6)
represonts a Cl-18 alkyl group including halogen-
substituted C1-18 alkyl, a C6-18 phenyl group in¢luding
substituted phenyl~, a group of the formula -0~(7)
~wherein, R(7) represents a substituted or unsubstituted
alkyl group or a substituted or unsubstituted aromatic
hydrocarbon group. As the substituent ~n the above-
15 mentioned alkyl or aromatic hydrocarbon group, there :~:
may be included alkyl groups, alkyloxy groups, aryloxy
groups, hydroxyl, amido group, carboxyl, carbamoyl
group, sulfamoyl group, halogen, acyl groups, acyloxy
groups 7 alkoxycarbonyl groups, alkoxyoxalyloxy groups
and the like The case having more preferable effectsin this in~ention is that R(7) is a substituted or
unsubsti.tuted Cl 15 alkyl group; that iS9 that R(7) is
an alkyl group such as methyl 9 isobutyl 9 a carboxyalkyl
group like ~-carboxyethyl; such alkyl, substituted with
a sulfamoyl group, a carbamoyl group or an aromatic
hydrocarbon group, as d-phenylcarbamoylethyl or d~
sulfamoylphenylcarbamoylethyl 9 a hydroxyalkyl group like
~-hydroxyethyl 9 an alkoxyalkyl group like methoxyethyl,
ethoxyethyl or ethoxyethoxyethyl; a halogen substituted
- 43 -
. . .
-~ 1$3~557~
1 alkyl group like chloroethyl7 alkyl substituted with an
amido or sulfonamido group 9 or alkyl substituted wi-th a
O 0 00
group of the formula o-c-~(6), ~OC-0-R(6), -oaCoR(5) or
-C-OR(6) (in the respective formulae, R(6) represents
a C1-18 alkyl group, a C6-18 phenyl group including
substituted phenyl), for examples, ethoxyoxalyloxyethyl
or ethoxycarbonylethyl,acetoxyethyl, and ethoxycarbonyloxy-
ethyl~, an amido group, an alkylamido group1 an arylamido
group (e.g. benzamido), a carbamoyl group, an alkyl-
carbamoyl group, an arylcarbamoyl group, a sul~amoylgroup, an alkylsulfamoyl group, or an arylsulfamoyl
group. Further, R(l) and R(2) may be bonded with each
other thereby to form a naphthalene nucleus. In this
case, X(5) may be bonded with any position of the
naphthalene nucleus
R(3) and R(4) each represent such group as
defined for the above-mentioned R(l), R(2) and R(5) or,
-the group of the formula -N-A3 ~ (X2)r-Ml]n~ In
formula, A3 is as defined before; that is, a substituted `
or unsubstituted aromatic hydrocarbon group or a
substituted or unsubstituted aromatic heterocyclic group?
preferably a substituted or unsubstituted aromatic hydro-
carbon group~ Ml, X2, Z', r and n are as defined before.
However, at least either one of R(3) and R(4) is the
Z'
25 group of the formula -~T-A~-(X2)r--Ml~ n- -
Xl in fornlula [XIV] represen-ts the same as Xl
_ ~.4. _
SS~?'9
l in the general formula ~I] 9 that is, a divalent group
and the most preferable as X1 is the group of the
formula.
R22 R22 ;,
l (J1)b-(E2)C ~(~T )d-J2-( N ~ f
(The symbols used here are the same as mentioned before.
Finally, w is an integer of l to 5.
While the compounds of the general formula
[XIV~ having more preferable effects in this invention
have been specified in detail in the preceding description,
much more preferable compounds are those wherein either
of R(3) or R(4) is the group of the above mentioned
Z'
formula -~-A3~ (X2)r-Ml]n (The most pre-ferable results
are obtained when A3 is a substituted or unsubstituted
phenyl groupO) While the other of R(3) and R(4) or at
least one among R(l), R(2) and R(5) is hydroxyl or -the
group of the above-mentioned formula -OCOY' or ~-oR(7)
(The most preferable results are obtained when the o-ther
of R(3) and R(4~ is hydroxyl.); Z' is an acyl group
containing the before-mentioned ~- or ~position halogen-
substituted Cl-5 alkyl or the group o-f the above-mentioned
O 00 ``
formula -COR23 or -aC-0-R24 (~he most preferable group
is trifluoroacetyl ) 7 and9 the total of m and n is 1.
The typical examples of the compound having the
general formula [I] or ~ which may be advantageously
I used -for this invention will be shown in the following
but it is n~t intended to limit the compou~ds of this
; invention thereto.
- 45 -
5S'7~
(1)
CII5 11
CONH(CH2)4-O~ 5 11
NHS0
NHCOCH2CH2~ N=N ~ OH
N-COCF3
b
(2)
OIIC,~l t
CONH( CH2 ) 4-O-~ C5Hll
NHSO;,~
NHSO2CH2CH2~N=N~ OH
N-COCF3
,:~
(3) :
c~ll t
GONH ( CH2 ) 4- ~,3 C5Hll-t
NHCoCHoCH2CH24~N=N ~} OH ~ . .
N-COCF3
(4)
CONII ( CE 2 ) ~- ~ C5111 1-t
NHS02 ~CH2C112~N=N~OH ' :,~
I~-COC~3
' .
-- 46 --
S~i7~
( 5 ) C H - t
~CONH(CH2),~-O~c5Hll_t
NHSo2~
NHS02~ CH2CH2~ N=N ~OH
N-COCF3
(6)
~CONE(Cn2)4-0~5Nll t
NHSO2 4 \~
NHCOCH2CH2~ N=N~ OH
COCF3 :'
~Cl
(7) .
~¢~CoNN(01~2)4-0~ C5Nll
HS2~; ~ / CH3 -
NHCOCH2CH2~ N=N~OH
N-COCF
(8) C~;Hll t
~CO~ll(C112)4-0~CS~
NHCOCH2CH2~N=N $~ OH
- ~7 -
-: - - ` . . -. .
( 9 ) C~ t
~CONH(CH2)4~0 e~C5Hll-t
NHS02~ CH2CH3
NHCOCH2C1~2-~ N=N ~--OH ~:
N-COCF
~3Br
(10) OH C~l-t
~-coNH(cH2)~ -o - ~ c5Hll
NHSO~--~ ,~CII2CH3
N~ICOCH2CH2--~3 N=N--~ OH -
N-COCCl_
~Br
~11) OH C5Hll-t
CO~H(CH2)4-0--~ C5Hll-t
NHS02~ CH2C~3
NHCOCH2CH2-~N=N~ CH2c~3
N COC~
~3 OH
(12) OHC5Hll-t
NH502~
NHCOCH2CH2~ N=N OH
Cl N-COCF
'
- -- 48 -- ~
~ `~
. .~
~ss~g
(13) C5~ t
~o~ o~
NH$02~ N=N OH
Cl N\COCP3
~ .
(14) C ~ t
CONH(CH2)4-O ~ ~ C5Hll
2~
N=N ~ OH `:
i~-COC~3
(15) C5llll-t
~_CONH(C~z)4-0~c5Hll-t
NXS2 ~ ~ Z 3
NHCOCH2CM2- ~ N=N- ~ -OH
; .
N-COCHC12
~ ~ Br
(16) OH C5Hll-t
CONH(CH2)4-O ~ 5 11
NHS02 ~
SO2NH - ~ N=N ~ -OX
N ~ F
- 49
iS7~
(17) OH C~l-t
~CONH(CH2)4-0--~ C5Hll-t
IIHCOCH2CHz~ =N--~OEI
N-COCCl
~--CF3
(18) OH C5E~ t
~¢~CONH(CH2)4-0--~3C5Hll t
2~
\~ NHCOCH2CH2~N=N~ OCOCH3
N-COCF3
( 19 ) CONH ( CH2 ) 4-0 ~ C5
NHSo24~ .~ -.,
MHCOCH2CH2 ~ Il=N-- ~ OCOCH
N~COCHC12
~Cl
- (20)
~ ~3 OH
N-C.OCF3 ~\~ CONH ( CH2 ) ~1 -
5 H11 t
CH2CH2CONH
- 50 - :
s~
( 21 ) CH2 CH3
OE / OH
--N=N~OCH
~N~ ~/ 3 ~1~ CONH(CH2)4-- :
3 ~ > ¢~ C5Hll t
2 2 5 11
(22)CH3 OIE 5 11
a~E3~ N-W--~7 OCH~ CONlE(clE2)~-O~c5}Ell t
O ~ ~ S2 II
CH2CH2CONH
NO
2 ~
(23) ~ ::
CH CH3
f~N=N~oCH3 OH C~l-t
N~\ ~C/OCE'3 ~CONH(CH2)4-0~ C5H11-t
6 5 ~ ~ SO2WEI
CH2CH2CNH
(24)
COCH3 CH~;
CH-N=N~ OCH7 OH C5~-t
~\E~ CONH( CH2 ) 4 -O~ c5Hll-t
CONIiC6H5 ~F3
CE2CH2CON~
- 51 - :
55'7~
(25 )
~N=N~ ~; 11
N-COCE'~ OH \'
~¢~CONf(Cif2)4-O~a5Hll
$02NEI
i.~2Ç)
N=N--~3
N-COCC13 OH G5Hll t
GONH( CH2 )4-O ~ C5
S2NH
(27)
N=N--~ C Hll-t
N-COCHC12 OH 5,~
NHS~¢~ COIJX ~ CH2 ) 4-O ~ 5 11
$02NH
(28)
~,COII f(Clf2)4-0~CS fll-t
2~ CX3
So2N:~3N=N~oC2H5
N-COCF3
Cl
- 52-
1~5S7~
,
(29) OH C ll-t
~CONU(C112)4-0~C5~11-t
NHSO2~ ,~,CH3
NHCOCII2CH2--~ N=N~
~3
Cl :
(30) C5~11~t
OH
CONH( CH2 ) 4-0~ C5Hll-t ,
NHCOCH2CH2
~3 ;.
NHCOCH3
(31) C Hll-t
~¢~CON (CE2)4-O~ 5 11
NHS02~ /C2H3'
~NHCOCH2CII2~N=N~
~13 `
:
(32)
CH3 N=N~
~H2 N-COC~3 Oll ~1
C II ~-N~S~CON~(CH2)4-0~ 5 11
S2~
~5~79
(33)
COIII~(C~2)4-0~C5~11-t
NHS02~ N~COCH2CX2--~--N=N~ OCX~;
~Cl
(34) C5Hll-t ~
~CONH(CH2)4-0~ C5Hll-t " . ~
NHSO2~ Cl
'~S02NH~N=N ~OC H
N-COCF3
~ 3Br
(55) ~ GO11H(C}l2)4-O~ 5 11
NHSO
~3 N=N~OCH3
H `
ph~N~ ~CC~ OH
~3~ ~coNN(cN2)4-o ~C5Hll t
S02NH
-- 54 ~ ~
557~
(37) C ~1 -t
OH
~CONH(CH2)~ 0~ ~ C51Ill-t
NHSO2~ CH3
~S02NH--e~3N._N~
N-COCE3 l~CON~I(CH ) o 5 11 t
~2~
~2NH C5Hll-t
(38) ~
~N=N~ OH 5 11
N02 A~COC~3 ~ CONH(CH2)4-O~c5
~NHSO~
~ S02NH
(39) C Hll-t
~¢~CONH(CHz)4-O~ 5 11
NHSO2~ ~ Cl `.
NHSO2~N=II~ OCH3
N~F3 . i
~Cl
(40) C5Hll-t
coNH(cH2)4-o ~ C5Hll-t
. ~NHCOCH2CH2~ ~H3
C~;
- 55 -
ss~
(41) C ~ l-t
~¢~CONH(CH2)4 -0~C5Hll .,
NHCOCH2CH2- ~ N=N ~ OCH3
2 3 .
'~
t42) OH 5 11
~CONH(CH2)4-0~c5xll-t
NHS2 4 ~ ~ OH
NHCOCli2CH2- ~ N=N ~
N-COCF3
OHC~5Hll-t
~43) ~ ~ ,CONH(C1~2)4-O ~ 5 11
CH3 ~ SO2NH
N=N-/ ~ OCH2CONH
~ F3
(44)
C~ ~ Cll2-N-Cll~ ~ ~ C'~3
( 3)3 2 1 OH . 3 ~ ~ EEal
CH3 Cl-
CE~ `
.
(45) ~ :
OH
31 15 ~ 0z- ~ CH2CH2 ~ M=N ~ OH
: N-COCF~
(46)
OH
n 131C15 ~ ~ CH2CH2 ~ N=N ~ OH
Cl ~ Cl N-COCF3
0~
(47)
OH
H2cH2coNHcl2H25
N-COCF3
NHS02 ~ CH2CH2 ~ N=N ~ OH
- N~COCF3
e~ ~
(48) -
OCH
33 16 S02NI~ ~ ~
OCH3 NHCOCH2CH2 ~ -N=N ~ OH
N\COCF3 ~ ;
~) ''
- 57 -
s~
(49)
n-H3~jC16-0~ \C=N-NHSO24~ ~ ' `` ;
(CHz)3 ~NHCoCH2CH2~3 N-cOCII
SO3H ~ 3
( 50) ~ ~ -
n-H29cl4-NHco-N~lNlI-so2 ~
NXCOCH2CH2~ N=N--~ OII
N-COCF3
_~ (51)
31 15 ~ SO2NHNHSO
NHCOCX2C~12-~ N=N~
N~ID3
(52) .
O
~I=N4~ OII 5 11
IIC~ Y ~ co~ (c~l~)4-o~c5
CH2CI12CONx ,' -~
.
;''
~ SiS79
(53)
OH 5Hll t
CNH(CH2)4-0~'5~11 t
NHS02~
~N=N~ :
~9 3
~<
(54)
OEI
e~ ~ n-H31 Cl 5 `~
N-COCF3
S02NH
~NEICO--
(55)
011
~¢~CONHC18H37
~)
N=N~ OH
N-COCF3
(56~ fOCF3
` C12H25-n '`
NHS02 Q
N=N~ OH
- N~F3 ~:.
`- 59- .
5~
(57)
OH \5 11
CoNlI ( GH2 ) q~-o -~c5~ t ' '
Cl ~-S021~H . :
~N=N-~ OCH2CONH
N-COCF3
~3
-:
(5~3) \5 11
CONI-I(C~2)~1-0~C5
N=N--~ OCH CONH~ 2
N- COCP~;
::
Cl
N~(c~l2)~-o~o5
--NHCOCH2CH2--~
N--N--~ OII
~OCE'~
~'.
Cl
~60)C51Ill-t
NHCOCH20 ~ C5Hll
~'NHS02~--N=N--~3 OH
N-COCF~;
_ ~0 -
.S57g
(61)
OH C5Hll t
CONH( CH2 ) 4-O ~ C5H
NHSO 2-~
\~(NHCOCH2CH2~ N=N~ OH
NH
(62)
0~1 C~ t
~¢~ CONII(CH2)4-O~C!5Hll-t
NHSO2~
02CH2C 2~N IT~OH
HN ~
è~s - ~
( 63 ) OH C5Hll-t
~o~ coNH ( cH2 ) 4-o~ c5 ~ t
NHSO2--~ C~3
NHCOCHOCH2CH2~ I`T=N~'~ OH
HN
(64) OX C5~ t
CONH(CH2)4-O ~ C5Hll-t
2 ~ J 2 2 ~ N=N ~ OH
HN
-- 61 --
7~
(65 ) OH C5Hll-t
CONH(CH2)4_o~C5 ~11 t
NHSO2~
\~NHSo2~3 CH2CH2--~--N=N ~ OH
HN
(66) C5~ t
~,CONH(CH2)4-O~ C51L~ll t
NHSO24~
\~ NHCOCH2CH2~ N=N ~ OH
~Cl
(67) 5 11
~¢~ CONH ( CH2 ) 4- è3 5 11
NHSO2--~ CH~
\=~ NHCOCH2CH2~ N=N~--OH
HN
( 68 ~ C H -t
OH 5~11
CONH ( CH2 ) 4-O--~ C5Hl l-t
NHS02~` NHCOC I CH ~ Il=N~ OH
~3C~3
- ~2 -
1~55'~
(69) OH 5 11
~¢~ CONH ( CH2 ) 4-O ~C5Hll t
NHSO2~ NHCOCH2CH2 ~ N=N ~ OH
HN
?~ Br
(70) C5Hll-t
~¢~CONH(CH2)~-0~c5Hll-t
NHS02 ~ NHCOCH2CH2 ~ N=N ~ OCE2CH~;
H ~:
~OH
NESO2~ a5 11 t
NHCCH2CI~2--~ N=N~ OH :~
Cl H
(72) OH C5Hll t
FCONE(C 2)4-o~C5}~1,
NIIS02~ N=N OH
Cl HN
-- 63 --
~SS~9 ~
(7~) C5~-t
~¢~ CONH ( CH2 ) 4-O ~ C5Hl1- t
llH$02~ ~
N=N~ OH
ElN
(74) C5~-t
~CONH(C~I2)4-O~C5Hll-t
NHSO --~
2 ~ SO2NH--~ N=N ~ OH ::
HN
~Cl
~75) 5 11
~, CONH( CH2 )4-~ C5Hll-t
NHSO2~ NHCO CE~2CI12~ N=N--~ O CO CE13
HN
~ '
(76 ) OH C5Hll-t
~, CONH(CH2)~!,-0~C5Hll-t'
NHSO--~
2 ~NHCOCH2CH2--~ N=N ~ OCOCH3
-- 64 --
iiS'7~
C5Hll-t
=N~3OH ~ C~ (cH?)4o~ 5 11
~S02NH
CH2CH2
(78) :~
OH CH2C113 Oli 5~ 11 t
~vi~ " l~o ~ OCH3 C~CONH( CH2 ~4---h C:~Hll-t
II ~ ~ 2
~< .
CH2CH2CONH
(79) OH 5 11
~ ~\f~CN~ 2)4-o~ c5~ -t
CH3 ~ =N~ OCH3
~ ~2
¢D CH2CH2CONH ~ ~,
N02
(80) OH C5~Hll
CH3 ,~CH3 I CONH(CH2)4.-0~C5Hll-t
~N=N ~ OC~13
O N OH NH
~3 2
C~12CH2CONH ~ .
'
- 65 -
sst~
(81) OH C5Hll t
f ~ ~,~,CONH(CII2)4-o~c5~ t
CH-N=I~ ~ O C 3
CONIIC6H5 ~~SO2NH
CH2C~2CNH
(82)
~N=N~ OH C5Hll-t
SHll-t
S02NlI , ,,
(83) . ~"
OH C5Hll-t
CONE( CH2 )4-O~ C5Hll-t
NHSO2--~ C~13.
2 ~3N=N~ 2 3
NH
Cl
(84)
OHC51l11~t
~CONH(CH2)4-0~ C5Hll-'~
Q NHCOCH2CH2~ ~H3
NH
~1 :'
-- 6 6
S57~
(85 ) C5Hll-t '
~¢rCNH(CH2)4-o~ 5 11
CH2CH2--~} ~CH3
NH
~ NHCOCH3
(86) C5Hll-t
CONH(CH2)4-0~ 5 11 t
~NHCOCH2CH2--~ ~ 2 5
HN
~Br
(87)
C~ 2)4- ~ c5~ t
( 88 ) C5~ t
~CONH(CH2)4-0~ C5Hll-t
NHCOCH2CH2~ N=N--~ OCH3
HN
Cl
~.
( ~39 ) C5Hl l-t
coNH(cH2)~-o~c5Hll-t ~;
~SO NH~ NH OC2H5
~13r
(90)
~N=N~OCi2 ~~2~ 5 11
,", ~3 ONH(CH2)~,0--~C51~ t ~;
H
~N~N~ OH C5~-t
Ph N ~ ~-~CONI~(C~2)4-~c5
- S02NH
(92)
OH 5 ll t
~¢~CONH(CH2)4,-0~C5Hll_t
NHS02~ CE~
2 ~ ~N~ OH C
H~ CoN~ ~ 5~ 11
~_ N~\f ' :
~SO2~ '
~.
- ~8- ~
;5 i79
(~3) :~
,
N=N~ OH C5H~t
2 ~¢~ CONN(CN2)4-O--~ 5
S02NH
(g4) C5Hll-t
,r~ Cl
NHSO N=N~OCN3 ~.
HN
~Cl
(95) C5Hll-t
CONH ( CH2 ) 4-O ~ C5~ t CH
I`THCOCH2CX2--~N=N~ OC 3
NH
~,~
C 3
(96) C H
OH 5 ll-
~¢~CONH(CH2~4-0--~C5X
NHCOCH2CX2~ N=N~ OCH3
HN
-69_ ~.
. .
(97)
~¢~ C 01111 ( cH2 ) ~l-O~ c5l~11-t
NHCOCH2CI17 ~N=N~
HN
,, ~3 .:
(98)
OI~ 5 11
~CONH(CH2)4-0~C5
--I~3 SO 2NH
~3 N=N--~ OCH2(,0~H :
~ r 3 N=N~ CH3
(CH3)3C-C~12 C Cl- ~ 3
'; ~100) , -:
OH
n-H3 1C15~ S2 {~ C~2CH2~ N=N~ OHi
:`
:
5S7~31
(101)
OH
n 31cl$`~o~cH2cH2 e3 N=N ~OH
C1~C1 \ : :,
OH
(102)
01
CH2CH2CONHC12H25
HN
O~NHS02-~ CH2CH2~-N~OH '
lIN
" .
(103)
OCH3
n-H33C16-S02NH--~ 2
OCH3 NHCOCH2CH2~,~N=N~O~
IIN
(104)
n-H33C16-0 ~ / C=N-NHS02
7 N~ICOCH2CT~2~
(CH2)3 N
S03H HN~
~.,~ ' '
-- 71 --
5S~ :
- (105)
n-H29C~ NHCO-NlINH-So2~
NIICOCT,I2CH2 e~ N=N ~ OH
HN
~106) ~ ~,
n-H31C15--;~ S02NHNHS02~ ,
NECOCH2CH2~ N=N~3 OH
HN
(107)
~N=N~ ~,~,CONH(CI~2)4-C~C5
~ S02NH
CH2CII2CONII
~.','
.
(108)
C5Hll-t
~,CONH(C 2)4-~ S 11 t
~N=
N~
IIN :
~Cl
.'
-- 7 2 --
,.
S79
( 109 ) ' '
lC15--
SO
2 NH
(110)
OH
¢ ~ CONHC1~3H~7
NHSo2-~9
~<NHcocH2cH2_~
N=N~ OH , ~
HN .:
:'
12 25
¢~ , :
NHso2~9 :`
N=N--~ dl~ ~
.~ ,
HN .:
,~
(112 )
OH
. ~COM~I(CH2)4-0
~S~ fC5~ t
- ~ N=N~--OC~2CONH 5 11
- 73 -
557~
.
(113) ~ ~ C~5Hll t
~¢;;~co~ (c.l2)4-4~cs1~ll-t
CH~ C113 ~502NH
~N=N-~OCH2CO H
HN , ~,
~ ':
~Cl :~
(11~)
OH C5Hll-t
~¢ CONH(CH2)~~0~ 5 11 :
NHS02~
N~COCH2CH2~ ,' '
N=N~ QH
IIN
Cl
( 115 ) C5Hll-t
NHCOCH20~ C5IIll-t
~LNHSO2--~ N=N~--OH ~ ~
O ~ ~.
~,
-- 74 --
~SS~79
1 The compounds of the general formula ~I] or
rII] used in the present invention are prepared accarding
to the following process.
The above-mentioned Z-substituted amine subs-ti-
tuted with two aromatic groups and a diazo compound ofan aromatic amine at least one of which aromatic groups
and amine has a reactlve jointing group are subjected to
a coupling reaction to prepare a shifted or non-shifted
azo dye having a reactive jointing group. Alternatively,
a diazo compound of the above-mentioned YC0-substituted
amine substituted with two aromatic groups (in which at
least either of the aromatic groups has a group of the
formula -I~H2) and a diazo coupler at least one of ~hich
aromatic groups and diazo coupler has a reactive jointing
group may be subjected to the coup]ing reaction to
prepare a shifted azo dye having a reactive jointing
; group.
Herein, the reactive jointing group means a
group competent to participate in formation of the ~
X2 or X3 moiety in the above-mentioned general formulae.
~ hen, the M1 or M2 moiety is introduced into
the azo dye having a reactive jointing group to obtain
a shifted or non-shifted DRX compound. Further, if the
(Ml or M2) - (gl, X2 or X3) moiety is introduced be-~ore-
hand into such compound as to be a diazotized compoundand/or a diazo coupler, a shifted or non-shifted DRR
compound may be obtained directly simply by the coupling
reaction as applied correspondingly to the above-mentioned
reaction. Furthermore, by using a Z-substituted amine
having or not having a reactive jointing group or the
.
, .
lS~i7~?
1 above-mentioned (Ml or M2)-(Xl, X2 or X3) moiety instead
of the above~mentioned amine substituted with two aromatic
groups, the above-mentioned reac-tion is carried out and
then at the suitable stage the reaction with a haloGen-
substituted aromatic compound may be c~rried out tointroduce an aromatic group into amino group afterw~rd,
thereby to obtain a shifted or non-shifted DRR compound.
In the above~mentioned reactions, when YCO is
no-t introduced into an amine group o-f the above-mentioned
aromatic group-substituted amine, the YaO group may be
introduced into the amine group ~e.g. acylated) at the
suitable stage of reaction to obtain a shifted DRR
compound. The shifted DRR compound may also be hydrolyzed
to obtain a non-shifted DRR compoundO
~hen, the particular examples of the process
for preparing the compound of the above-mentioned general
formula ~I] or [II~ used in this inventionO
Synthetic Example 1 - Preparation of the exemplified
compound (1)
5.0 g of ~-4-aminophenylpropionic acid was
dissolved into 100 ml of water containing 20 ml of conc.
hydrochloric acid. Into the resulting solution, 10 ml
of an aqueous solution containing 2.~ g of sodium ni-trite
was poured at 0 - 5C~ After stirring for 20 minutes
the reaction mixture was added with 0.2 g of sulfamic
acid and then with 20.0 g of sodium ace~tate
On the other hand, 5.7 g of ~-anilinophenol was
added with 15 ml of trifluoroacetic acid and 15 ml of
trifluoroacetic anhydride and the mixture was subjected
~0 to the reflux ~or one hourO Under a reduced pressure,
76 -
7~
1 excess of the trifluoroacetic acid and trifluoroacetic
unhydride were distilled off and the residue was
dissolved into 100 ml of ethanol. This solution was
added with aqueous ammonia. While the resulting solution
was kept at about pH 9, the above-mentioned diazonium
salt solution was poured thereinto. After stirring for
30 minutes, the mixture was neutralized with an acetic
acid and the resulting oily material was extracted by
use of ethyl acetate. After washe~ with water, -the
resulting solution was dried and the solvent was removed.
The residual oily material was purified by silica gel
column chromatography to obtain 8.6 g of a pale yellow
ma-terial having m.p. 161--165C, as shown in the following
formula:
Compound (A)
HOOCCH2CH2 ~ N=N ~ OH
~aoaF3 ' .
0.9 g of Compound (A) and 1.3 g of the compound
of the following forrnulao
Compound (B) ~;
OH C5Hll-t
'^'~ -Co~E(~H2)~0--~ a,,Hll t
l~HS02~
2 -
were dissolved into ~ ml of tetrahydrofuran. The r~sult-
ing solution was added under ice cooling conditions
77 -
S57~
1 with 1 ml of a tetrahydro~uran solution containing 004 g
of dic~clohexylcarbodiimide and the mix-ture was stirred
for four hours. Further, stirring was continued a-t a
room -temperature for -four hours to prepare a white
precipitate. ~he precipitate was collected c~nd the
filtrate was concentrated and purified by silica gel
chromatography Then reprecipitation was carried out in
ethyleneglycolmonomethylether-water to obtain 0.74 ~ of
a pale yellow material having m.p. 107-112C ~compound
10 (1)~
Synthetic ~xample 2 - Preparation of co~lpound (1)
0.9 g of the above-mentioned Compound (A) and
1.3 g of the above Compound (B) were added with 5 ml of
a dimethylformamide solution containing N-ethoxycarbonyl-
2-ethoxy-1,3-dihydroquinolineO ~.f-ter the admixture was
stirred a-t a room temperature for 6 hours, it was cooled
in an ice bath and -then added with 50 ml of an aqueous
solution containing 1.5 g of sodium hydrogen carbonate.
The resulting precipitate was coLlected, washed with
water and dried. The precipitate was purified by silica
gel column chromatography. The resulting material was
re-precipita-ted frorn ethyleneglycolmonomethylether-water
to obtain 0.82 g of a pale yellow material having m,p.
104-110C [compound (1)].
Synthetic Example 3 - Preparation of compound (61)
2.0 g of the above-mentioned Compound (A) was
dissolved into 60 ml of ethyl alcohol and the solution
was added with 2 ml of 2N potassium hydroxide a~ueous
solution. The mixture was stirred at a room temperature
~0 for 30 minutes and then neutralized with an acetic acid
- 7~ -
I.SSi79
1 and extracted with ethyl acetate. The extracted solution
was was~ed with water, dried7 concen-trated and -then
purified by silica gel column chromato~raphy. 1'he eluate
is distilled to remove the solvent and then added with
n-hexane to obtain 1.2 g of reddish brown crystals having
m.p. 138-141C as shown in the folloT~Jing formulaO
Compound (C)
HOOC~H2CH2 ~ N=N ~ OH
NH
0.7 g of Compound (C) and 1.3 g of Compound (B)
were dissolved into 3 ml of tetrahydrofuran. The
mixture was added under ice cooling conditions with 1 ml
of a tetrahydrofuran solution containing 0.4 g of
dicyclohexylcarbodiimide and stirred for four hours.
The stirring was continued at a room temperature for
four hours. The white precipitate formed was collected
and the filtrate was concentrated and purlfied by silica
gel column chromatographyO ~urther~ the reprecipitation
was carried out using ethyleneglycolmonomethylether-
water to obtain 0.86 g of a yellow material having
. .
m.p. 102~106C [compo~md (61)].
Synthetic Example 4 - Preparation of compound (61)
003 g of compound (1) was dissolved into 10 ml
of ethyleneglycolmonomethylether. The solution was added
with 0.5 ml of 2N KOH aqueous solution and stirred at a
room tempera-ture for 10 minutes. The mixture was
neutralized with an acetic acid and added with water.
- 79 -
5S~7~
1 The precipitate was filtered, washed with water, dried
and then purified by silica gel column chromatography.
The re-precipitation was carried out using ethylene-
glyco.Lmonomethylether water to obtain 0.2 g of a yellow
materiaL having m.p. 103-107C [compound (61)~o
Thus, -the various compounds of the above
general. formula ~I] or [II] may be prepared in such
manner as above. Among the said compounds thus prepared,
the compounds were subjected to the measurement of ~n
elementary analysis to show the results, as follows~
- 80 -
,
1~55791
0~ 0 N r~ ~ ~ 0 0 N
0 ~0 ~ 0 ~1 IS~ ~ ~ NCO :~ 1~ 0 0 ~J
~i C~ D r~ Dt~
h ~~1 ~ N 0 Ir~ OJ O ~ ~1 ~ ~1
~ ~ O~ ~ O ~ O C~ ~ ~ 0
~ LO Ll~ ~ ~O 15~ ~ ~O 15~
~e ~
_ 0 0 ~ ~ U~ ~ ~ ~~I Lr~ 0~ o
~q ~ U~ ~ o ~ ~ ~t ~ 0 ~~ U~
.~ ~ O C~ O ~ ~ O~O U~ C\~
P ~ ~o ~o ~o ~ O~ ~ ~ ~O ~O
3 ~
~ ~ ~ ~ O ~ O ~ O U~ ~ ~D 0 ~ ~ U~
a) ~ ~ ~ ~ ~ o ~ ~D ~ O
.
.
0 ~ O ~D L~ ~r~ I d t--
~ N ~ 0 ~~
C~ ~D t~ Ir~ C) 1~ N1~ ~D ~ N
~ ~O ~
O ~ ~ ~ o` ~_1 N ~ ~
C~
- 81 -
l~S~9
N C~~0 t~i Lr~ 0 N. ~ O.~ . ~ ~ 1--
0 ~o O
~I
U`~ 0 ~ 0 ~ 0 ~t<~t-- Lr\ 0 C~ ~-- ~ O U~ L
~ t\J C~~O cr, o~ ~ ~ o ~ G' ~ ~D 0 --1 ~t G~
Ls~ L~`\ Lr\ Ll~ L~ Lr~ U~ Ll~ ~O L~ Lr'\ Lt~ L~\ Lf~ ~O Lf~ Li'`
G~ ~O O~ J 0t-- L~ ~ 0 r l r-l N
Ll~ O ~ ~ ~1 ~ O CJ~~\1 1~ (~ G~ G' i~ 0 el
0 L~t~ L~ Ll~t~ cn N~1 Ir~ ~0 O N
O ~ ~ ~ O ~O ~O Lt~ O ~) ~ O ~O
L~ 0GL GL OL ~ ~ ~ O L~ ai~ ) N O ~D L~
G'a~ G~ O cr, 0 0 G' ~r-l Lf~ ~D 0
O1-- 01~ 0 ~D O
0 0 r-J ~~ Lr~ ~ N ~a~ N ~O --~ ~1 1~ ~I N O
~ ~ 03 Lr~CO00~D 0cr~ L;~ t ~ Lr\ L~ o ~ u~
Lr\ Lr~ L~ Lr~ Lr\ L~ L~ L~ Lr~ Lr~ Lr~ L~ Lt~ Lr~ ~7 L~ L~
o ~ o ~D ~ Lr~ ~1 ~ ~I L~ ~O ~ O
t-- N O ~\1 G~ d- N O ~ L~ 0 ~0 If~ Lr~
... .......... .
O ~ 0 Lr~ D Lr~ t ~ O N I--i LS'\ ~D O N
O ~ O ~ ~ O ~D ~O ~ ~D
`': ~.'
~O ~ 0 ~ O ~1 ~ ~r~ GL L~ 0 c;~ o
~1 ~1 ~Jrl N N N N N N N N N N
.
-- 82 --
' ~
s~
N 0 ~ O Ll~ l i~ O O ~ d'0~ --1 r~ D ~ r-l
O ~0( ~ 0 N ~ ~ ~0 11~ 1-- r~
1~ ~o1~ C~ 0~ot~ 0 0
--l 0r-l ~ ~ ~11~ ~ --1 0 r-l r-l ~\ N r~ 0
r l (U ~ a:~ ~D.0 03 ~1 0 l-- O ~
':
~ ~I r~ ~ 0 ~ ~ 0 0 ~ r~ ~ O~ O U~
0 ~0a~ ~ ~'tCO 1~ ~-1 N Or~ 0
.
~O L~ O ~ ~O ~ ~~O ~ ~O ~O ~O~O ~ ~
~ r-l N 0~ r-l \D Lf~Li~r~l O d- r- ~~1 ~ (~ N
a~ a) 0 ~-~ o ~ 0 ~ ;t ~ N ~ t-- t-- ~ ;~
Lt`\ ~ N 1~ ~ ~ O ~ L~ NO
O~OLt~ O ~O~O Lt~ ~O ~O
r-l O 0`~ r-l ~ O ~t ~ t~ N r-l ~ N r-l 0 ~0 C--
~0 ~ ~ N OC-- C~ 0 ~ l O N
~O 1~ O ~O ~O~O~O ~O ~O ~O ~O ~D ~O ~O ~O ~ ~O
~\ ~\t `\ ;~ ~\ ~ ~ G~ ~t ~t 't ~t ~t ~t ~t G'' ;;t
~ 83 -
~ ~5i5'7~
0~ ~ 0 ~ ~~ u~ u~ c~ ~ ~ r~ . .
~i 0 ~ ~ ~ ~ ~~ 0 0 0 ~ ~ ~ 0
. .
~ N 0 N~ 1 ~1 ~I NN ~ Lf\ a~` O~
N N ~ U~ C5~ NLl~ G' C~ ~ D ~ C-- ~--O O ~'
-- 0 01'~t~\N 0`.L~ O N ~ ~ ~) `.
N ~ ~1 1~ 0 r-N~57 N C-- N N U~~1
~ . . . . . . . .
O ~ '~ ~ O ~ N N C~) ~
; '
- .:
: .
N O C~ O O--1 G- O ~1 ~IN O O O O ~ 1--l
tD N~ OL'~ ~ G' L~ a~Lr~ N G' ~ ~D N
,~ co r- r- r- c~ ~ ~ r- r- ~ 0 0 ~ r- t~ co
Ci`\ ~ I--l N ~ G' a~ r- o~ 0 r-- N C)~ --1 ~I N O
N O L" ~O ~ G~ N G' ~ L'~ '~t L" N r-- r-- N N
.~ ........ . , ,
~O ~O Ll`\L'~ D L'~L'~ 11~ L'~ Lr~
N ~0 ~ O 0 N~~0 N r- Lr~ L~ O Ll~
O G' ~)t ~O ~ ~0 0~) t~ 0 d- r- ~ ~ ~ o
~i L~ D 0 ~~--~ ~ O ~) N N 0 0
~) ~O~O~S:)L'~ O ~ r-
' :
O ~I N t<~ G' L~ ~D ~ 0; ) Ci~ O r-l N ~ d' L~
li~ L~ L~ 15`\ Ll~ L~ L~ L~ L'~ L'~
-- 84 --
~5~
0 Ll~ O Ir~ r-l CO ~ 0 U~ 0 0 ~-1 N O Ci~
1~ Ll~ CO 0 0 Lr~ ~5) ~ O ~0 N t ~
0 ~~ ~ 0 ~ ~ 0 0 ~ --I :
0 NC~~ ~ ~I_ N 0 0C~ ~ O 0 0
t<~ N 0 0 N1~ 0 0 ~N ~Lr~O Or~
t-- ~ O O O NLt~ O ~CJ~ r-l 01--lr-l ~ 1~ ~1
o ~ ~~ ~ ~1 ~a) o
o r--u~o ~u~ ~ oc~
~ ~D ~ ~~D ~ ~~O ~~ ~~ ~ t~ O ~O
0 11~C-- Nt~C-- O 1~ lr~ 0 0~ii 0 ~ CO 1~ t<~
~ 0~a~ 01~(~ ~-1~1 0Lt~ ~0 ~c-- 0
0 ~~ ~ ~ ~ ~ 0 0 ~0 0,,~0 0
~ N~O~ 0 0tS~ J O0 ~
. ~ . . . ~ . .. . . . .
DU~~1 ~ t~ 0 NN ~D ~ OL(~ O C~)
N1~ 0 0(~ ~ ~ N CO~D 0
O C~ O ~L~ or- ~D 0 0tS~
O ~ O~O ~ D1~ O~O
.
~ 0(~O~I Nt~ 0~ 0C~ O ~ N
.
- ~5 -
S~
Lr~ N N N O Lt~ , N C~i ~ILr~ r--i O ~ a~ 0
O N 15~ 0 0 N t ~ ~D ~t 0 tl~ O ~ 0 ~t O
co a~ 1~ r 1 1~t'--0 ~\ L-- C~) t-- 0 a) 0 0 0 L~
`,,
O L~ C-- 0 1~ ~ N OLr~ a~ ~ ~ 0NN L t~
~O ~O ~O L~ ~O Ll'\ ~O Ll~ U) L~ L5~ ~O ~O ~O ~D ~O ~O
N Ll~ Lr~ t~ ~ L~ C~ Lr~ N O ~O O L~ L~ a~ ,~ o
~I N ~ 1~ N 0 CS~ N C)`\ l-- Ll~ O 0~ ~) ~. O C~
~) Lr~ ~x) a~a~ 0 ~; Lr~ ~ r i O r~ N
1~ ~D ~ ~O ~ O ~O ~O ~ ~ C~
0 ~1 ~ ) 0 0 ~ ~t Lr~ ~Ot ~ O ~ (~'
N ~ r~ Lr~ C~Lr~ r-l ~t~I N r~ O r-/
C~: ~ ~ ~ L-- t-- C:) C~ L-- C~ 1-- 0 0 ~ 0 O~
L~ ~ N a~ 0 t~ ~I t~--t Gt O N r-- ~D
Gt ~0 N O G'' ~ ~a~Gt t-- Lr~ G' L~
~o ~ ~0 ~0 ~0 L5~~0 LS~ ~0LS~ 3 ~ 0
~1 ~t N N a~ O 't --t ~DGL ~ IS~ N LS~ ~t
-- 0 Lt~ ~ ~t 0 ) . C-- 0 0 ~ Gt
C~ O ~L) Lr~ 0 O 0(X~GL L~ i O I--i O N Ci~
O ~O ~O ~D ~O ~D ~O 1
GL Ln ~ 0 ~ O r--~N 1~\ GLL~ ~:) 1~ 0 ~ ~
0 a) 0 0 ) 0 c~ ~ O
_ ~36 -
.
iS7~
t-- ~ cr 0 0 ~ ~-~ ~ o o t-- o ~ ~ 0
o o ~ 0 t
~ a~0 ~~ ~0c-- 00 ~1 0 ~ 0 0
~O ~IS~ ~ O ~U~ r~ ~ N O~
t~ I~ 0~~It-- O~1 O C~ r-l r J ;-~ r-)/
~O ~ O1--~O~O ~O [`-~O 1~ ~O ~) ~O ~O
Cj~r-lr-~O1~~ O ~ O t~
U~ ~t Ot~J~015~ ~ 0 N . 1~ ~ t~
.. ..
O r-l~t~L~L~ ~ ~~ 0 0 r-- 0 0 0
o~D~O~D~O ~O r- ~o ~D ~O ~O ~D ,,
OOt~~ 0 ~ O r ~ ~
(~J ~0~ 0~ 0~0~ -! 1~ r~ l 0
u~ O~ X a~ ~ ~ ~ ~ c~ co .~ 0 a) 0 0
~D 0~O 0 O ~D O ~t t~l 0~ I0~ r-l O
0~ .D ~ 0rl ~ Or~ 1 O ~
.
~O ~ O ~ ~O ~ ~O ~ ~ ~ O ~D
~ ~J r-(rJ~t ~O ~ t~i~ ~ ~1O~ U`\ O~
CO r-l r-~ OIr~~t ~ :;.' O~ 0 C ) ~ O L
O r~ ~ ~ Ll~ IS~ O~ 1-- ~ O 0 t-- 0 0 C~)
1~~O ~ O ~O ~O
O O OO O O OO O r-l r-~ r~ r-l r-l ~1
r-~ r-l r-~r~r-lr-l~I r-l r-l r-l r~ r-l ~I r-~ r l
87 -
` ~ ` . .. .
~557~
The present invention will be explained in further :.
detail.
The photographic element of this invention comprises
at least a photosensitive element containing a silver halide
emulsion layer and a compound of the above-mentioned general
formula [I] or [II] as a DRR compound.
More particularly, the invention relates to a color
diffusion transfer photographic element which comprises a
silver halide emulsion layer and a yellow dye image-forming
compound represented by the formula:
R(l) R(2)
[Ml~(Xl)q ~ Al'-N=N ~ R(3) ` :
R ~ (R ))w
wherein Al' represents an aromatic hydrocarbon group or an
aromatic heterocyclic group R(1), R( ) and R(5) each repre-
sent hydrogen, halogen, nitro, an alkyl group, hydroxyl,
alkoxy and aryloxy, a group of the formula -OCOY~ (herein, the
O- in the -OCOY' group represents a hydrolyzable group); R(3)
is as defined with respect to R( ), R( ) and R( ), or the group
Z'
; -N-A3 [ (X2 ~ Ml]n'
and R(4) represents the group
Z'
-N-A3 ~ X2 ~ Ml]n'
in which A3 is an aromatic hydrocarbon group or an aromatic
heterocyclic group; X2 is a divalent joint group; Z' is
hydrogen or the group YC0- (the YC0- is a hydrolyzable group);
Ml is a monovalent dye releasable group Xl is a divalent
joint group; q is 0 or 1; m is 0 or a positive integer, n is
an integer not less than l; r is 0 or 1; and w is an integer
from 1 to 4.
~ - 88 -
'7g
The silver halide emulsion is a hydrophilic
colloidal dispersion of silver bromide, silver iodide,
silver chloride, silver iodobromide, silver chlorobromide,
silver chloroiodide, silver chloroiodobromide, or the
mixture of these silver halides. The emulsion may
include, in addition to conventional emulsions, those
which are prepared in various processes, such as the
so-called conversion emulsions, Lippmann emulsions and
direct positive emulsions like ones fogged beforehand or
of the internal latent image type~ And, the grain size,
content, a mixture ratio or the like of silver halide
differs according to the kind of a photographic element.
As a hydrophilic protective colloid which is a binder
for silver halide, there may be used various natural or
synthetic materials such as gelatin, gelatin derivatives
or polyvinvyalcohol, etc., singly or in combination.
The silver halide may chemically be sensitized
by using active gelatin, a sulfur sensitizing agent such
as allylthiocarbamide, thiourea, cystine, etc.' a selenium
sensitizing agent, and/or a noble metal sensitizing agent
such as gold, ruthenium, rhodium, iridium, etc~' singly
or in suitable combination. Further~ the silver halide
emulsion may also be sensitized optically, for example,
- 8~a -
~g
1 by using cyanine dyes or merocyanine dyes. Gener~lly a
light sensitive silver halide color photosensitive
element may be p,epared by using three kinds of silver
halide emulsions whieh respectively have light sensitivi-ties
different in wavslength region.
'~he silver halide emulsion may be stabilized by
triazoles, tetrazoles, imidazoles, azaindenes, quaternary
benzothiazolium compounds, zine compounds or cadmium
compounds and may eontain a sensitizing eompound of e.g.
quaternary ammonium salt type or polyethyleneglyeol type.
The emulsion may eontain a sultable gelatin plasticizer
sueh as glycerol, dihydroxyalkane like 19 5-pentanediole,
ethylenebisglycolic acid ester, bis-ethoxydiethylene-
glyeolsuccina-te, polyacrylic amide latex and, further9
eontain a gelatin hardening agent such as formaldehyde,
a halogen-substituted fatty acid like mucobromic acid, a
compound having an anhydride group, dicarboxylie chloride,
a methanesulfonic acid biester or a so~lium disulfite
derivative of dialdehyde wherein the aldehyde groups are
separa-ted by 2 or 3 carbon atoms; a coating aid sueh as
saponin, and sulfosueeinate 7 or other various photographie
additives. Moreover, if desired, the emulsion may
contain various other additives ordinally used in
conventional photography such as an antifoggant or an
ultraviolet absorber.
In this invention, various kinds of silver
halide emulsions may be used as mentioned above. In
ease using a nega-tive silver halide emulsion, a negative
color diffusion transfer image may be obtained. A
positive color diffusion transfer image can be obtained
_ ~9 _
~15~i7~
1 in various processes.
~ or example, the processes include such process
using a direct positive silver halide emulsion as
disclosed in U.S. Patents 3,227,552, 2,592,250, 2,0057~37,
3,3S7 ? 778 and 3,761,276, Brltish Pa-tent 1,011,062,
Japanese Patent Publication No. 17,184/66 and Japanese
Laid-Open-to-Public Patent Publication ~o. 8,52~/75,
such process using physical developmen-t ~s disclosed in
British Patent 904,364 and Japanese ~aid-Open-to~Public
Patent Publication No. 325/72, and such process using a
negative silver halide emulsion layer con-talning a
compound releasing a developmen-t inhibi-tor by reacting
with an oxidation product o-E a developing agent while
a fogged emulsion layer adjacent to the negative
emulsion layer is added with a color image ~orming
ma-terial, as disclosed ln Japanese Patent Publication
No. 21,778/68 and U.S. Patents 3,227,554 and 3,632~345.
A positive color dif~usion transfer image may
be prepared in various processes as described above.
Preferred is a process using a direct positive silver
halide emulsionO One example of the direct positive
silver halide emulsion, is a silver halide emulsion which
is developable b~ subjecting beforehand to exposure over
its whole surface or chemical process but becomes to be
imagewise non-developable by imagewise exposure.
Another example of the direct positive silver
halide emulsion is a direct positive silver halide
emulsion having light sensitivity mainly inside silver
halide grainsO In this invention, the latter direct
positive silver halide emulsion is pre~erable. In this
-- ~0 --
S7~
1 direct positive silver halide emulsion9 latent images may
be formed mainly inside the silver halide grains by
imagewise exposure and the surface development under
fogging conditions causes the formation of positive
5 silver images.
There are various processes for such development
under the fogging conditions. ~or example, there may be
used the so called air fogging developer as disclosed in
W. German Patent 850,383 and U,S. patenJG 2,497,875, or
the flash exposure over the whole surface at the time o~
development The latter process are disclosed in
W. German Patent 854,888, U.S. Patent 29592,298 and
British Patents 1,150,553, 1,195,838 and 1,187,0290
Further, it is possible to carry out development in
15 the presence of a fogging agent. As a fogging agent used
for such case 9 there rnay be used hydrazine type compounds
and N-substituted ~uaternary ammonium salts singly or
in combination. These fogging agents are disclosed in
U.S. Patents 2,58~,982, 3,227,552, 3,61596159 3971~,494,
20 3,734,738 and 3,718,470. Although the amount of a
fogging agen-t may be selected within a wide range -
depending on the use purpose, it is generally 0.1-2~0 g
based on one liter of a developing solution in case of
adding into the developing solution and 0.01-0. 2 g/m2 in
25 case of adding into a photosensitive element~
In this invention, the photosensitive element
comprises a combination of the above-mentioned silver
halide emulsion and the compound of the above general
~ormula ~I~ or ~ as a DRR compoundO ~y using one or
30 two of such combinations of sllver halide emulsions and
-- 91 --
S~'7~
1 DRR compounds, there may be obtained a unicolor dye image
or a l~icolor dye image, for example, ~or quasi-color
photograph. And, in case of usin~ for a color diffusion
trans-~er process, for example, according to a multi-color
substraction process, blue light sensitive, green light
sensitive and red light sensitive silver halide emulsions
are combined as associated with yellow, magenta and cyan
DRR compounds respectively.
A preferable multi-layered construction comprises
successively the blue light sensitive emulsion layer, the
green light sensitive emulsion layer and the red light
sensitive emulsion layer from the exposure side. In
this case, a yellow filter layer may be placed between
the blue light sensitive emulsion and the green light
sensitive emulsion. As an example of process for
combining the light sensitive silver halide emulsion and
the DRR compound, there may be a process adding them
separately into the layers adjacent to each other. ~ut,
in case of using such short wavelength shi~t type D~R
compound as having the group of the ~ormula YC0 as Z in
the general form~a ~I~ or ~ , it is possible to add
said DRR compound into the silver halide emulsion bscause
the DRR compound does not reduce the sensitivity of the
emulsion.
Further, there may be such mixing packet
process where not less than two combinations of the
silver halide emulsions and the DRR compounds are
presented in one layer, as disclosed in U.S. Patents
2,800,458 and 3,466 9 662.
The DRl~ compound used in this invention is
- 92 -
~5~17~
1 dissolved in as small an amount of organic solvent as
possible and dispersed into a hydrophilic protective
colloid, such as gelatin or polyvinylalcohol, wh;ich is a
binder of the silver halide emulsion layer or its
adjacent layer in the photosensitive element. As the
organic solvent, there may be used a high boiling;solvent,
a low boiling solvent which may be removed away by
evaporation, or an organic solvent easily soluble in
water, singly or in combination.
As a particularly useful high boiling solvent
in this invention, there may be included ~-n-butyl-
acetanilide, diethyllaurylamide, dibutyleaurylamide,
dibutylphthalate and tricresylphosphate. As a useful
low boiling solvent, there may be included ethyl acetate,
methyl acetate and cyclohexanone. These low boi]ing
solvents can be removed by evaporation at the time of
drying after coatin~ to form a layer or may be removed
before coating in the manner as disclosed in U.S. Patent
2,801,171.
As an organic solvent easily soluble in w~ter,
there may be used 2-methoxyethanol and dimethylformamide.
Instead of or in addition to the high boiling
solvent, various lipophilic polymers may be used. As
the lipophilic polymer, there may be used polyvinyl
acetates, polyacrylic esters and polyester of polyhydric
alcohol and polybasic acid.
In this invention, useful for dispersing the
DRR compound of this invention is such process as
disclosed in Japanese Patent Publication Nos. 13,837/68
and 32,131/73, U.S. Patent 3,832,173 and Japanese ~aid-
- 93 -
SS'7~
1 Open-to-Public Patent Publication No, 17,637/75,
Among the compounds of the above-mentioned
general formula ~I] or ~II], the D~R compounds having a
water soluble group such as a carboxylic group or a sul-~o
group may be dissolved into water or an aqueous alkaline
solution and then dispersed into a hydro~hilic protective
colloid and, if necessary, it may be neutralized.
~ he amount of the DRR compound used in this
invention may be selected within a wide range according
to the kind of compounds to be used and desired results.
For example, it is preferable to use about 0.5~0 to
about 10~ by weight of the compound in the water soluble
organic colloid coating solution as used.
In case of carrying out a multi-color diffusion
15 transfer process, it is advantageous to use inter layers
in a photographic element. The inter layer comprises
gelatin, polyacrylamide, calcium alginate, partial
hydroly~ate o~ polyvinyl acetate, a hydrophilic polymer -~
like hydroxypropylcellulose, or such polymer, formed from
20 a latex of a hydrophilic polymer and a hydrophobious
- polymer, as disclosed in U.S. Patent 39625J685.
~urthert usable for the inter layer may be
such compounds as disclosed in UOS Patents 3,384,483, - .
3,421,892, 3,427,158, 3,121,011, 3,0439692~ 3,059,263j
25 3,615,422, 3,625,685, 3,756,816 and 3,069,2640
In order to avoid color mixing or color
contamination due to diffusion of an oxidation product
of a developing agent into other layers9 it is preferable
to add, into the inter layer or a layer between a silver
30 halide emulsion layer and an image receiving layer in a
94
~557~
1 photographic elemen-t, a coupler, such amidra~one ompound
as disclosed in Japanese ~aid-Open-to-Public Patent
Publica-tion No. 15,532/73, such hydrazone compound as
disclosed in W. German Pa-ten-t 2,123,2689 or a non-
di-ffusible hydroquinone derivative. The non-diffusible
hydroquinone derivative may further be added into a
silver halide e~ulsion layerO
As a support for a photosensitive element of
this invention, there may be used various natural or
synthe-tic polymers such as paper, glass9 cellulose
nitrate, cellulose acetate, polyvinylacetal, polycarbonate,
polystyrene, polyethylene terephthalate, polyprop~lene
and polyethylene. These may be transparent or opaque
depending on the use purpose.
~urther, a vapor permeable support or an oxygen ;~
barrier support as disclosed in U ~. Patent 3,573,04~
may be used advantageously. Moveover~ in case of using
a transparent support, it is preferable tha-t the support
is colored to such an extent as not to prevent an
exposure and visual observation of formed images but to
avoid fogging of an emulsion layer at the -time of
processing due to piping light coming in -from the sides
of the support.
In this invention, the above~mentioned photo-
graphic element was exposed imagewise and then the photo~sensitive element was developed in the presence of the
below-mentioned silver halide developing agent combined
with the below-mentioned alL~aline processing solution.
By this development, the compound of the above general
~0 formula ~I~ or ~ and other D~R compounds placed in the
- g5 -
~:1557~
1 photosensitive element release diffusible dyes imagewise.
These diffusible dyes are diffusion-trans~erred to an
image receiving layer which is placed in a superposed
relation with the above-men~tioned photosensit,ive element
at least during the development and then dyed in the
image receiving layer, to prepare color images I-t is
preferable for the image receiving layer to contain a
mordant. ~;
As -the mordant suitable to the image receiving
layer, there may be used any of those which have a
preferable mordanting effect on the diffusible dyes or
their precursors on way of their diffusion transfer~
Useful are such as poly-4-vinylpyridine9 poly-4-vinyl-N~
benzylpyridinium-p-toluenesulphonate and cetyl -trime-thyl
ammonium bromide~ The mordant which may be advantageously
used in this invention includes such as disclosed in
U.S. Patent 29882,156, Belgian Patent 729,202, UOS~
Patents 3,488,706, 3,859,096, 3,788,855, 3~227,1~
~,271,147, 3,709,690, 3,625,69~, 3,770,439 and 3,7569814,
and Japanese ~aid-open-to~public Paten-t Publication
No. 61,228/75.
The above-mentioned mordant is generally used
in various binders such as gelatin, polyvinylalcohol9
polyvinylpyrrolidone or wholly or partially hydrolyzed
celluloseesterO Solely such binders having a mordan-ting
e-~fect as poly-N-methyl-2-vinylpyridine9 ~T-methoxymethyl-
poly hexylmethyleneadipamide, a copolymer or polymeric
mixture of vinylalcohol and N-vinylpyrrolidone, partially
hydrolyzed polyvinylacetate, acetylcellulose, gelatin9
polyvinylalcohol or a guanylhydrazone derivative of
96 -
1L 5 ~
1 acylstyrene polymer may be used for an image receiving
layer as far as the mordant is concerned.
As a special example 9 the mordant may be
contained in the alkaline processing solution as
5 disclosed in Japanese ~aid-open-to-public Patent
Publica-tion No 47~ 626/750
The image receiving layer may also contain an
ultraviolet absorbing agent, a fluorescent whitening
agent or various o-ther additives ordinarlly used for
convelltional photography.
After forma-tion of dye images is substantially
accomplished following a diffusion transfer of diffusible
dyes due to application of an alXaline processing
solution, it is necessary to reduce a pH within a pho-to-
15 graphic element to about neutrality, so that thestability of the dye images is augmented and additional
image formation is substantially stopped to inhibit
discoloration or contamination of the images as caused
at a high pH. Therefore, it is advantageous -to use a
20 neutralizing layer containing such material as reducing
the pH sufficiently. As the material, for example, such ~ r
polymeric acid, its partial ester or anhydride as
disclosed in U.S. Patent 3~ 362 ~ 819~ such higher fatty
acid as disclosed in UOS. Paten-t 2~983~606 and such
25 metallic salt of solid acid as disclosed in U.S. Patent
2 ~ 584 ~ 030 are useful in this invention.
Further, microcapsulation as disclosed in U S~
Patent 3~576~625 may be carried out.
It is preferable, moreover, to use a timing
layer in order to control a reducing speed of the p~Io
- 97 ~
iS~
1 As the material for said layer, there may be used, ~or
example, gelatin, hydroxypropylcellulose~ partially
hydrolyzed vinyl acetate-acryl latex, polyacrylamide,
acetylcellulose, polyvinylalcohol, partlally acetalized
5 polyvinylalcohol and the mixture o~ these~ This timing ;
layer is usually employed in combination with a
neutralizing layer. ~he combination may be placed on a
support of a photosensitive or image-receiving element
or a support of cover sheet which sheet will be
explained later. Ordinarily, the timing layer is
positioned between the neutralizing layer and a space in
which an alkaline solution is spread.
~ he alkaline processing solution used in -this
invention contains a component necessary to develop the
silver halide emulsion and form the di~ usible dyes and
has a high alkalinity, generally at more than pH 10.
The alkaline processing solution used in this
invention contains an alkali metal or alkaline earth
metal hydroxide such as sodium hydroxide, potassium
hydroxide, calcium hydroxide and lithium hvdroxide, or
sodium carbonate or diethylamine
It is pre~erable, moreover, that the alkaline
processing solution contains a silver halide developing
agent.
As the silver halide developing agent used in
this invention, there may be included, ~or example,
hydroquinone, l-phenyl-3 pyrazolidone~ 1-phenyl-4,4-
dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-
hydroxymethyl-3-pyrazolidone, ascorbic acid, aminophenol,
N-methylaminophenol~ N,N-die-thyl-p-phenylenediamine,
- 98 -
~S~
1 3-meth~ T,~-diethyl~p-phenylenediamine and 3-methoxy-
~-e-thyl-N-ethoxy-p-phenylenediamine.
Although various silver halide developing
agents may be used as mentioned above, a black-and-white
silver halide developing agent i 3 particularly preferred
to reduce possible co-ntamination at areas where the dye
images are formed. Although the above-mentioned silver
halide developing agent is generally contained in the
alkaline processing solution, it may also be contained
beforehand in a photographic element. Further, it may be
also contained both in the alkaline processing solution
and in the pho-tographic element. In case of containing
said agent beforeb~and in the photographic elemen-t, it
may be contained in the form of its precursor.
It is also preferable that the alkaline solution
is added with such compound as hydroxye-thylcellulose or
carboxymethylcellulose sodium salt. `
~ ur-thermore, the alkaline processing solution
~ay be added with such compound (suitab~e to improve
; 20 photographic properties) as a sodium sulfite, potassium
bromide, a triazole type compound or a mercapto type
compound.
Although the above-mentioned alkaline processing
solution may be applied in various ways to the pho-to-
sensitive element, it is preferable that -the solution
is held in a rupturable container and is applied to the
exposed photosensitive element af-ter exposure by rupturing
said container by means of pressing materials equipped
in a camera and/or a cartridge for a photographic element~
~0 As a rupturable container, such container as
_ 99 _ :
~55'7~
1 disclosed in U.S. Patents 2,543,181, 2,643,886, 2,72~ 9 051,
3,056,492 and ~,152,515 may be used~
In addition to -the above-mentioned photo-
sensitive element, the photographic element in this
invention may comprise an image receiving element and a
rupturable container, while the photosensitive element
and an image receiving layer of the image receiving
element may be placed as separate before exposure or
both may be combined as one body to form a unit. After
the processing, the photosensitive element and the image
receiving element may be combined as one body or the
photosensitive element and the image receiving element
may be stripped off from each other~
In the case that the film unit was used in such
process as placing the photosensitive element and the
image receiving element detachedly before the exposure
or as stripping away the photosensitive element and -the
image receiving element from each other, it is required
to form the image receiving layer on another support
which is not common to that of the photosensitive element.
As the support for the image receiving layer in the image
receiving element, the same material as for the support
of the photosensitive element may be used and it may be
transparent or opaque.
The image receiving layer may also be formed on
the support of the photosensitive element and in this
case it is preferable ordinarily to use the so-called
cover sheet, in order to spread the alkaline processing
solution between the cover sheet and the photographic
~0 element. As the support of the cover sheet, there may
,
57g
1 also be used the same as the photosensitive element.
It is good to form, as a background for formed
images, a light reflecting layer having a high white~
ness. Although the position o~ the light reflecting
layer is not par-ticularly restricted, it is good to form
the light reflecting layer between the photosensitive
element and the image receiving element ln the case that
the photosensitive element and the image receiving
element are not stripped off from each other after
processing. The light reflecting layer may be formed
beforehand as a layer or such layer may be formed between
the photosensitive element and the image receiving
element at the time of processing by providing a light
reflec-ting agent in the alkaline processing solution.
As -the light reflecting agent, there may be used titanium
dioxide, zinc oxide, barium sulfate9 flake silver,
alumina, barium stearate or ~irconium oxide, singly or
in mixture of two or more kinds. In case of forming
beforehand the layer, the said agent may be dispersed
into an alkaline solution-compatible binder, such as
gelatin, polyvinylalcohol or any other suitable binder.
As a process for forming the light reflecting
layer9 for example, such process as disclosed in Japanese
~aid-open-to-public Patent Publication ~os. 486/71 and
477/72 may be used.
The above-mentioned light reflecting layer may
also be added with a whitening agent such as stilbene or
coumarin~ In case of developing the silver halide
emulsion under room light after exposure9 it is preferable
to provide an opacifying layer in order to protect the
- 101 -
... . ~.
: :
557~
1 silver halide emulsion from undesired light exposure.
The opacifying layer may be formed beforehand as a layer
or formed at the time of processing. As the opaci-fying
agent, there may be u7ed carbon black or such indicator
dye as disclosed in Japanese ~aid-open-to-pub]ic Patent
Publication Nos. 26/72, 27/72 and 28~72. It is also
advantageous to use such desensitizer as disclosed in
U S Patent 3,579,333.
The light reflecting layer and -the opacifying
agent layer, bo-th as mentioned above, may be presented
as the same layer or as separate layers adjacent to each
other.
Although various layer arrangements as the
photographic element may be used, such element as dis-
closed in U S. Patents 3,415,644, 3,4159645~ 3~415,646,3,473,925, 3,57~,042, ~,57~,043, 3,59~J164, 3,594,165~
3,615,421, 3,576,626, 3,658,524l 3,635,707, 3,672,890,
3,730,718, 3,701,656 and 3,689,262, Japanese Laid-open-
to-public Patent Publication ~o. 6,337/75 and Belgian
Patents 757,959 and 7579960, may be used in this
invention.
In the above-mentioned various film units~ if
desired, a -filter dye suitable to improve photographic
properties may be added at any position of the exposure
25 side of the silver halide emulsion. As the filter dye,
those which are stable at an ordinary pH but become
colorless due to decomposition or the like~ when they
contact with the alkaline processing solution may be used.
A-fter the diffusion transfer of dye images to
3Q the image receiving layer is carried out9 there remain
- 102 -
S~
1 the images of silver images and dyes or dye precursors
in the photosensitive element as a func~ion of the
diffusion transferred images. If this ~ilver or residual
silver h~lide is removed by processing in a bleaching
bath and then in a fixing bath or in a bleaching-fixing
bath while the dye precursor is transferred to a dye,
there may also be the dye images reversed from the dye
images formed on the image receiving layer.
x ~ le_l
Photosensitive element (I) was prepared by
successively forming the following layers on a transparent
polyethyleneterephthalate film support having the thick-
ness of 110 ~m:
(1) A layer having the dry thickness of 1.1 ~m, contain-
ing a blue-light sensitive silver iodobromide emulsion
in a silver amount of 11.3 mg/100 cm2 and a gelatin
amount of 122 mg/100 cm2,
(2) A layer having the dry -thickness of 1.5 ~m, contain~
ing compound (1) in an amount o-f 8.0 mg/100 cm2,
tricresyl phosphate in an amount of 4~0 mg/100 cm2 ~nd
gelatin in an amount of 14.0 mg/100 cm2, and
(3) A protective layer having the dry -thickness of
OO9~m, containing 10.0 mg/100 cm2 of unhardened gelatin~
Then~ photographic elements (II), (III), (IV),
(V) and (VI) were prepared by carrying ou-t the same
procedures in the case of photographic elemen-t (I),
except that, instead of compound (1) used in preparation
of the said element (I) 9 compolmds (6) 9 (9), (61), (66)
and (69) were respectively used.
Those layers of the photosensitive elements
- 103 -
LSS7~
1 which contain the compounds o~` the invention were
prepared in the following manner; at first, dissolving
the compounds individually into e-thyl acetate an~
tricresyl phosphate, dispersing the resulting solution
in an aqueous gelatin solution containing ~lkanol~
(Du Pont de Nemours & Co.) as a surfactant and then
coating the dispersion.
Next, image receiving elements were prepared
by successively forming the following layers on a
cellulose acetate-coated baryta paper supportO
(1) A neutralizing layer having the dry thickness of
25.0 ~m, containing 24.8 mg/100 cm2 of polyacrylic acid,
(2) A timing layer having the dry thickness of 3.0 ~m,
containing 5.0 mg/100 cm2 o-f cellulose acetate, and
(3) An image receiving layer having the dry thickness
of about 20 ~m, containing 22.0 mO/100 cm2 of a copolymer
of styrene and ~T-benzyl-~T/N-dimethyl-N-(3-maleimidepropyl)
a~noniurn chloride at the ratio of 1019 and 22.0 mg/100 cm2
of gelatin.
Photosensitive elements (I) to (VI) were exposed
from the support side through a 30-step silver wedge with
each density difference of 0.15. Then, the exposed
photosensitive elements were superposed on the above-
mentioned image receiving element while 1 0 ml of the
~ollowing alkaline processing solution was spread there-
between, thereby to carry out the processing~
Alkaline Processing Solution
Potasslum hydroxide 28.0 g
Sodium sulfite 1.0 g
1-Phenyl-3-pyrazolidone 4.0 g ;
:'
- 104 -
~5~
l 5-Methylbenzotriazole 1.4 g
Carbon black (MA-100 by
Mitsubishi Chemical Industries, Ltd.) lOO.O g
Sodium carboxy methylcellulose 50.0 g
Benzyl alcohol 5.0 ml
Distilled water -to make total1000 0 ml
.
After two minutes, the image receiving elements were
stripped off from the photosensitive elements and dried.
The reflection density of the trans~er images thus
obtained was measured by use of a blue filter to
determine their maximum densities (Dmax) and minimum
densities (Dmin) as followso
Photographic
_Element _ max. _~min.
(I) l.90 0.22
(II) 1087 0.21
(III) 1.97 0 23
(IV) 1093 0.22
~V) 2.01 0.23
(VI) 1.86 0.20
On the other hand, then, photosensitive elements (I) to
~VI) were exposed in the same manner as above except but
from the opposite side of the support. ~fter two minutes~
the image receiving elements were stripped off frQm the -~
photosensitive elements and dried~ The reflecting
density of the transfer images thus ob-tained was measured
by use of a blue filter. The data obtained were compared
with those in the cases of the exposure from the support
side to show a reduction ratio in sensitivity, as
followso
- 105 -
5S79
1 Photographic
Element ,`.-~ lo~ E
(I) 0.06
(II) 0,05
(III~ o.og
(IV) 2.30
(V) 2.~3
(VI) 2.47 :
From the above result, it w~s understood that
photosensitive elements (I), (II) and (III) using
respectively compounds (1), (6) and (9)9 which are the
shift type DRR compounds, showed a remarkably small
decrease in sensitivity in comparison with photographic
elements (IV), (V) and (VI) using such non-shift type
DRR compounds as compounds (61), (66) and (G9).
The similar result was also o~tained by using,
in the case of forming the layers of above photosensiti~e
elements (I) to (VI) containing the compounds, the '
following procedures The compounds were di.ssolved into ~':
acetone; the resulting solutions were filtered to remove
those insoluble in acetone9 the resulting filtrates were
poured into water to deposit the above-mentioned
compounds9 the deposits were collected by filtration9
the masses thus obtained were washed with wa-ter9 7 wt/% ;~
of the exemplified compounds were added to water
containing 0.7 wto~ of Alkanol-XC to prepare aqueous
slurries9 the slurries were dispersed by means of a
supersonic homogenizer into an aqueous gelatin solutions,
- and, the coating thereof was carried out,
,.~
- 106 ~
5st;~9
1 Exam~le 2
._
A multi-layered multicolor photosensitive
element ~as prepared by successively forming -the following
la~ers on one side of a ;oolyethylene terephthalate film
support having the thickness of llO/~m, on the other side
of which was coated with a layer of 25 mg/100 cm2 of
carbon black and 45.0 mg/100 cm2 of gelatino
(1) A layer having the dry thickness of 1.5 ~m, contain-
ing 13.2 mg/100 cm2 of a cyan DRR compound having the
following formulao
OH C5Hll-t
CONH (CH2 ) 40--~ C5~ 't
2~ ';
~ ~02NH
02N~N=N~
2 ~ :
and 17.0 mg/100 cm2 of gelatin,
(2) A layer having the dry -thickness of 1.4 ~m, contain-
ing 1403 mg/100 cm2 (as silver amount) of a red light-
sensitive, internal latent image type silver iodobromide
emulsio.n, 0.7 mg/l.OO cm2 of potassium 2-octadecylhydro-
quinone-5-sulfonate, 0.14 mg/100 cm2 of form.yl-4'-
methylphenylhydrazide and 15.5 mg/100 cm2 of gelatin~
(3) An inter layer having the dry thickness of 1.0 ~m~
containing 6.0 mg/100 cm2 of 2,5~di-tert-octylhydrGquinone,
6.0 mg/100 cm2 of di n-butyl phthalate ~d 12.0 mg/100 cm2 ~.
of gelatin,
(4) A layer having the dry thickness of 1.3 ~m, containing
- 107 -
~sstS~
1 10.O mg/100 cm2 of a magenta DRR compound having the
following formulao
OH C5Hll t
CoNH(cH2)4o ~ C5H11 t
l`~HS02~ ~
~IHCO~HCh~5
O
I OCH
OH ~2NH2
and 15.0 mg/100 cm2 of gelatin,
(5) A layer having the dry thickness of 1.4 ~m, contain-
ing 14.0 mg/100 cm2 (as silver amount) of a green light
sensitive, internal latent image type silver iodobromide ~i
emulsion, 1.0 mg/100 cm2 of potassium 2-octadecylhydro-
quinone-5-sulfonate, 0.1~ mg/]OO cm2 of -formy]-4'-
methylphenylhydrazide and 15.5 mg/100 cm2 of gelatin~
(6) An inter layer having the dry thickness of 1.0 ~m,
containing 6.0 mg/100 cm2 of 2,5-di-tert oc-tylhydroquinone,
6.0 mg/100 cm2 of di-n-butyl phthalate and 12~0 mg/100 cm
of gelatin, ~ ;~
(7) A layer having the dry thickness of 1.1 ~m, contain-
ing 8.~ mg/100 cm2 of compound (61) and 12.5 mg/100 cm2
of gelatin,
(8) A layer having the dry thickness of 105/,~m, contain-
ing 140 5 mg/100 cm2 (as silver amo~mt) of a blue light
sensitive, internal latent image type silver iodobromide
emulsion, 0~7 mg/lOO cm2 of potassium 2-oc-tadecylhydro-
quinone~5-sulfonate, 0~14 mg/lOO cm2 of formyl-4'~
- 108 ~
:~1557~
1 methylphenylhydrazide and 16.1 mg/100 cm2 of gelatin,
and
(9) A protective layer having the dry thickness of
009 ~m, containlng 10.0 mg/100 cm2 of gelatin.
In the above-mentioned multi-laye~ed multicolor
photosensitive element, the dispersion of the cyan DRR
compound, the magenta DRR compound and compound (61) was
carried out in the following mannerD The cyan DRR
compound, the magenta compound or compound (61) was
dissolved into acetone; the resulting solution was
filtered to remove any insoluble into acetone; the
resulting filtrate was poured into 125 ml of water to
deposit the said compound 9 the deposit was collected by
filtratlon and washed with water9 the aqueous slurry
containing 7 wt. ~ of the cya~l DRR compound, the
magenta DRR compound or compound (61) and 0.7 wt. ~o of
Alkanol-XC was prepared9 and, the slurry was dispersed
by means of a supersonic homegenizer in-to an aqueous
gelatin solution.
Next, an image receiving element was prepared
by successively forming the following layers on a
transparent polyethyleneterephthalate film support
having the thickness of about 100 ~mO
(1) A neutralizing layer having the dry thickness of
25 25.0 ~Im, containing 24.8 mg/100 cm2 of polyacrylic acid,
(2) A timing layar having the dry thickness of 300 ~m, ``:
containing 5~0 mg/100 cm2 of cellulose acetate, and
(3) An image receiving layer having the dry thicknes~ of
about 200 ~m, containing 22.0 mg/100 cm2 of a copolymer
of s-tyrene and N-benzyl-N,N-dimethyl-N-(3-Maleimidepropyl)
-- 109 --
~5~ii'7~
1 ammonium chloride at the ratio of lol, aMd 22.0 mg/100 cm2
of gelatin.
The multi-layered multicolor photosensitive
element thus prepared was exposed wedgewise through blue,
green, red, yellow, magenta and cyan filters aMd -the~
superposed with the above-mentioned image receiving
element, while a rupturable container containing 1.0 ml
of an alkaline processing solution of the following
composition was placed therebetween, thereby to form a
photographic element.
Then, the above photographic element was passed
through an opening of about 80 ~m between one pair of
jux-taposed press rollers to rupture the container and
spread its contents between the photosensitive element
and the image receiving element.
Alkaline Processing Solutiono
Potassium hydroxide 56 g
Sodium sulfite 2.0 g
l-Phenyl-3-pyrazolidone 8.0 g
5-Methylbenzotriazole 2.8 g ~;
TitaMium dioxide 40.0 g
Sodium carboxymethylcellulose 50.0 g
Distilled water to make up total 1000.0 ml
After about 8-10 minutes, the good dye image
was observed through the transparent support of the
above-described image receiving elementO
~xample 3
A layered multicolor photosensitive and image
receiving element was prepared by successively forming
the following layers on a traMsparent polyethylene-
- 110 -
5~'7~ ;
1 -terephthalate film support having the thickness of
100 t~m.
~1) An image receiving layer having the dry thickness
of 2.0 ~m, containing 22 mg/100 cm2 o~ a copolymer of
styrene and N-vinylbenzyl-N,~,N-trihexylammonium chloride
at the ratio of 1 1, and 22 mg/100 cm2 of gelatin,
(2) A light reflecting layer having the dry thick~ess
of 7 ~m, containing 220 mg/100 cm2 of tita~ium dio~ide
and 22 mg/100 cm2 o~ gela-tin,
(3) An opacifying layer having the dry -thickness of
4 ~m, containing 20.5 mg/100 cm2 of carbon black and
42.0 mg/100 cm2 of gelatin,
(4) A layer having -the dry thickness of 205 ~m,
containing 14.3 mg/100 cm2 (as silver amount) of a red
light sensitive, internal latent image type silver
iodobromide emulsion, 0.7 mg/100 cm2 of potassium 2~
octadecylhydroquinone-5-sulfonate, 0.14 mg/100 cm2 of
formyl-4'-methylphenylhydra~idel 800 mg/100 cm2 of a
cyan DRR compound having the following formula
OH a 5Hll-t
= ~O~H(C~I2)40 ~ C5Hll-t
~IHS02~
So2NH~
02N~N=N~ OCOCH~
S02CH~
4.0 mg/100 cm2 of -tricresyl phosphate and 22.5 mg/100 cm2
of gelatin,
~ 111 -
5~
1 (5) An inter layer having the dry thickness OL loO ~m9
containing 6.0 mg/100 cm~ of 2,5-di-tert octylhydro-
~quinone, 6.0 mg/100 cm2 of di--n-butyl phthalate and
12.0 mg/100 cm2 of gelatin,
(6) A layer having the dry thickness of 2.7 ~m, con-tain-
ing 14.0 mg/100 cm' (as silver a~nount) o~ a green light
sensitive internal latent image type silver iodobromide
emulsion, 1.0 mg/100 cm2 of potassium 2~octadecylhydro-
quinone-5-sul~onate, 0~13 mg/100 cm2 o~ formyl-4'- `
10 methylphenylhydrazide, 10.0 mg/100 cm2 of a magenta D~R
compound having the following formula ~;
OE ~5Hllt :~:
- CoNH(cH2)4o- ~ -C5Hllt
NHS02~ .
~ N-N ~ -OCOOC2H5
CH~jS0
i~
5 0 mg/100 cm2 of tricresyl phosphate and 25.3 mg/100 cm2~-
of gelatinj
(7) An inter layer having the dry thickness of 1.0 ~m,
: 15 containing 6.0 mg/100 cm2 of 2,5-di~tert-oc-tylhydroquinone,
6~0 mg/100 cm2 of di-n-butyl phthalateg 3.5 mg/100 cm2 of
yellow colloidal silver and 1200 mg/100 cm2 of gelatin,
(8) A layer having the dry -thickness of 2.7 ~m, ~;
containing 14~5 mg/100 cm2 (as silver amount) of a blue
light sensitive9 internal latent image type silver
iodobromide emulsion, 0 7 mg/100 cm2 of potassium 2-
octadecylhydroquinone-5-sulfonate, 0l14 mg/100 cm2 of
- 112
5S7~
1 formyl-4' methylphenylhydrazide, 13.0 mg/100 cm2 o-f
compound (1), 6.0 mg/100 cm2 of tricresyl phosphate and
26.0 mg/100 cm2 of gelatin, an~
(9) A protectiv~ layer having the dry thickness of
0.9 ~m, containing 10.0 mg/100 cm2 of gelatin.
The layers containing a cyan D~ compound9 a
magenta DRR compound and compound (1) were formed in
the following manner- The cyan D~ compound, the
magenta DRR compound or compound (1) was dissolved into
ethyl acetate and tricresyl phosphate 9 the resulting
solution was dispersed in an aqueous gelatin solution
containing Alkanol-XC (Du Pont de ~emours & CoO); on
the other hand, the water-methanol (lol) solution of
potassium 2-octadecylhydroquinone-5-sulfonate was
dispersed into an aqueous gelatin solution containing
Alkanol-XC; the dispersions thus obtained were mixed
into the internal latent image type silver iodobromide
emulsion containing a methanol solution of formyl~
methylhenylhydrazide just before -lhe coating was
carried out.
Next, a cover sheet was prepared by successively
forming the following layers on a transparent polyethylene-
terephthalate film support having the thickness of
100 ~mO
(1) A neutralizing layer having the dry thickness of
25.0 ~m, containing 25.1 mg/100 cm2 of polyacrylic acid,
and
(2) A timin~ layer having the dry thickness of 3.0 ~m,
containing of 5.5 mg/100 cm2 of cellulose acetateO
The layered multicolor photosensitive and image
- 113
1 receiving element thus prepared was exposed wedgewise
through blue, green, red, yellow, magenta and cyan
-~ilters and then superposed with the cover sheet, ~hile
a rupturable container containing 1.0 ml of an alkaline ~;
processing solution having the composition set forth
below, was placed therebetween~ thereby to form a photo-
graphic element.
Then9 the above photographi.c element was
passed through an opening of about 80 ~ between one
pair of juxtaposed press rollers -to rupture the
container and spread its conte~ts between the photo-
sensitive and image receiving element and the cover ~.
sheet.
Alkaline Processing Solution~
Potassium hydroxide 56 g
; Sodium sulfite 2.0 g
l-Phenyl-3-pyrazolidone 3~0 g
5-Methylbenzotriazole 2.8 g
Carbon black (MA-100 by
Mitsubishi Chemical Industries~ Ltd.) 100.0 g
Sodium carbogymethylcellulose 50.0 g
Benzylalcohol 10.0 ml ;~
Distilled water to make up total1000.0 ml
hfter about 8 ~10 minutes, the good dye image
was obser~ed through the transparent support of the
above-mentioned photographic element~
- 114 - :
