Note: Descriptions are shown in the official language in which they were submitted.
s
1 BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photographic light-
sensitive sheet ~or the color diffusion transfer process and,
more particularly, to a silver halide photographic liyht-sensitive
sheet for the color diffusion transfer process containiny a dye
image providing material having a novel redox moiety.
2. Description of the Prior Art
Color diffusion transfer color image forming processes
using a dye releasing redox compound are described in ~apanese
Patent Application (OPI) No. 104343/1976 (The term "OPI" as used
herein refers to a "published unexamined Japanese patent
apllication"), U.S. Patents 3,932,381, 3,942,987, 3,928,312,
3,931,144, 3,954,476 and Research Disclosure, No. 13024 (1957).
The term "dye releasing redox compound" means a compound
containing therein a group referred to as a redox moiety and a
dye or a dye precursor moiety. The redox moiety renders the
redox compound immobile due to a ballast group attached thereto,
but under alkaline conditions the compound splits and releases
a compound having the dye moiety (a dye compound). For instance,
when a light-sensitive element having a light-sensitive silver
halide emulsion layer and a dye-releasing redox compound
associated therewith is exposed and developed with an alkaline
processing solution, the redox moiety per se is oxidized in
proportion to the amount of developed silver halide and the
compound splits into a compound having a dye moiety and a non
diffusible quinone compound. As a result, the compound having
a dye moiety diffuses into an image-receiving layer to provide
a transferred image therein.
Examples of dye-releasing redox compounds which release
~3~3S
1 magenta dyes are described :in U.S. Paten-ts 3,932,3~0 and 3,931,1
etc. Elowever, technical problems are encountered, using these
magenta dye releasing redox compounds specif:ically described in
such prior art, in that the transferred images have insufficient
stability. For example, the light fastness of the images is not
adequate and the ima~es fade to a large extent even in a dark
place. Also, the transfer of the dye compound is not adequate.
For instance, with respect to the fading-in-dark of
transferred dye images, it has been known that unreacted monomer
(such as acrylic acid, butyl acrylate, etc.) in the neutralizing
layer containing a polymer acid such as polyacrylic acid, a
copolymer of acrylic acid and butyl acrylate, etc., as disclosed
in U.S. Patent 3,362,819 hereinafter described, adversely
influences to the fading of transferred dye images. It has
also been found upon further investigation that unreacted butyl
acrylate monomer exceptionally degrades magenta dye images
:- obtained from prior art dye-releasing redox compounds such as
described in U.S. Patent 3,932,380. However, it is extremely
difficult from a technical standpoint to limit the amount of
unreacted monomer during the synthesis of polymer acid for a
neutralizing layer to an extent that it does not adversely
influence the light fastness of the images. Therefore, it has
been desired to develop a redox compound which releases a dye
compound which is less sensitive to such a monomer.
Furthermore, it has also been found upon further
investigation that using these prior art dye-releasing redox
compounds discussed above, the visual spectxum of the transferred
image is too wide to affect good color reproduction.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide
1 a dye imaye providing ~aterial which provides a stable magenta
dye image.
A second object of the present invention is to provide
a dye image providing material having a dye moiety whose color
hue is excellent.
A third object of the present invention is to provide
a dye image providing material which provides a transferred
dye image which does not change hue with pH.
A fourth object of the present invention is to provide
a photographic light-sensitive sheet for the color diffusion
transfer process containing a dye image providing material which
provides a transferred magenta dye image having a sufficiently
high optical density in the presence of a relatively small amount
of silver halide.
A fifth object of the present invention is to provide
a so-called "negative utilizable" photographic light-sensitive
sheet for the color diffusion transfer process in which a light-
sensitive element is also utilized.
A sixth object of the present invention is to provide
an intermediate of such a dye image-providing material.
The inventors have conducted various investigations
and found that the above-described objects are effectively
attained by a photographic light-sensitive sheet wïth satisfac-
tory photographic properties for the color diffusion transfer
process which contains a dye image providing material represented
by the following general formula:
G
N=N J\/ ~ ~ Rla-O-R2a
J-l~qXl~}mY
~3~3S
1 and preferably by the following formulae (I) and (II):
OH
Q2 ~ o-Rla-o-R2a (I)
OH
Q ~ 0-Rla-O-R2a (II)
S2 NH~// ~ o-Rlb-o-R2b
wherein Q represents a hydrogen atom, a halogen atom, a sulfamoyl
group represented by ~e formula ~S02NR3R4 wherein R3 represents a
hydrogen`atom, an alkyl group including substituted and unsubsti-
~uted alkyl groups; R4 represented a hydrogen atom, an alkyl group,
including substituted and unsubstituted alkyl groups, an aralkyl
group or an aryl group; and R3 and R4 may combine directly or
through an oxygen atom to form a ring; a group represented by the
formula -So2R5 wherein R5 represents an alkyl group,including sub-
stituted and unsubstituted alkyl groups or a benzyl group; a carboxy
group, a group represented by the formula -COOR6 wherein R6
represents an alkyl group, including substituted and unsubstituted
alkyl groups, a phenyl group or a substituted phenyl-group; or
a group represented by the formula -CoNR3R4 wherein R3 and R
each has the same meaning as defined above; Q2 is positioned at
the 5- or the 8-position to the hydroxy group and represents
a hydroxy group, a group represented by the formula -NHCOR a or
a group represented by the formula -NHSo2R4a wherein R4a has
the same meaning as R defined above, except for the absence of
~13~
1 a hYdrogen atom; m is O or 1; ~ is O or l; J represents a
divalent group selected from a sul~onyl group and a carbonyl
group; Z represents a hydrogen atom, an alkyl group or a
substituted alkyl group; Xl represents a divalent bonding group
represented by the formula -Al-(L)n~(A2)p- wherein Al and A2
are the same or different and each represents an alkylene group
or an arylene group; L represents a divalent group selected from
an oxy group, a carbonyl group, a carboxyamido group, a
.carbamoyl group, a sulfonamido group, a sulfamoyl group, a
sulfinyl group and a sulfonyl group; and n and p each represents
~ or l; G represents a hydroxyl group, a salt thereof, or a
hydrolyzable acyloxy group represented by the formula
O O
-OCE or -OCOE wherein E represents an alkyl group, including su~-
stituted and unsubstituted alkyl groups, or an aryl group; Rla
and Rlb, which may be the same or different, each represents an
alkylene group having 2 or more, preferably 2 to 8, carbon atoms;
R and R2b~ which may be the same or different, each represents
an alkyl group including unsubstituted as well as substituted
alkyl groups; and Y represents a molety which releases or provides,
as a result of development processing under alkaline conditions,
an azo dye having a different diffusibility from that of said
dye image-providing material.
DETAILED DESCRIPTION OF THE INVENTION
. ~ . . . _ . .. . .
In the description hereinafter, the terms Rl and R2
la d Rlb and R2a and R2b, respectively, u
otherwise indicated.
In the above-described general formulas, the compound
is characterized by the presence of the -O-Rl--O-R2 group in the
dye moiety, more particularly the moiety corresponding to the
~L~3~5
1 diazo component~ The O_Rla_O_R2a group positioned at the
4-position to the azo group and the -S02NH- group (Y in the
formula (I)) positioned at the 3-position is another character-
istic. In particular, in the compound represented by the
formula ~I), it is important that the -0-R a-0-R group and Y
be positioned ortho to each other. It is believed that due to
this structural feature, the function of Y as a redox moiety is
intensified and, t~us, the dye compound is effectively released
from the dye-releasing redox compound resulting in improved
transferability. In fact, improved transferability (particularly
improved transferability at a low pH) is not observed where the
relative position of these two groups is different from that of
the present invention. For example, where the -0-R -0-R a
group is positioned at the 2-position with respect to the azo
~roup and Y is positioned at the 5-position with respect to the
azo group, improved transferability is not obtained.
- Likewise, the presence of the -0-R b-0-R2b group and
Y ortho to each other is important in the compound represented
by the formula (II). Due to this fact, the effect that the
hue of a transferred image from the compound of the formula (II)
does not change with a change in pH. Although there are various
hypotheses for such improvement, one reason is the presence of
an intramolecular hydrogen bond as shown in ~ormula below which
suppresses dissociation of -S02NH.
-N=N ~ / \ 2
' H~
In fact, it has been found that the hue of the transferrea image
s
1 changes with a chanye in pH, where the relative position o~ these
two groups is differellt than that of the present invention, for
example, when the -O-~la-O-R2a group is positioned at the
2-position to the azo group and Y is positioned at the 5-position
to the azo group, even though the -O-R~a-O-R2a is present.
It is also recognized that a visual spectrum of a
transferred image formed from the compound of the present inven-
tion is sharp which exerts a favorable influence on the color
reproduction.
The alkylene group having 2 or more carbon atoms
represented by Rl can be a straight chain or branched chain
alkylene group and an alkylene group having 2 to 4 carbon atoms
is preferred. Although Rl can be a branched chain alkylene group,
a branched chain alkylene group which forms an acetal linkage,
i.e., a -O-C-O-R2 linkage, is excluded. Particularly preferred
examples of Rl are a straight chain alkylene group represented
:- by the formula -(CH2)p-, wherein p is an integer of 2 to 4, and
a branched chain alkylene group having 3 to 4 carbon atoms such
as -CH(CH3)CH2- and -CH2CH2CH(CH3)- with an alkylene group which
forms an acetal linkage being excluded as described above. In
view of easy availability of starting materials to produce the
dye image providing material of this invention, a -CH2CH2- group
is pàrticularly advantageous for Rl. When Rl represents a
methylene group~ an acetal linkage, in this case a -O-C~I2-0-R2
linkage, is formed, which is undesirable since it is chemically
unstable, particularly under acidic conditions, and tends to
decompose during the preparation thereof. For the same reason,
groups where two oxygen atoms are bonded to the same carbon atom
in the -O-Rl--O-R group (i.e., forming an acetal linkage), are
also not desirable.
,. .
. The alkyl yroup represented by ~2 can be an unsubsti-
tuted or substi~uted straight chain or branche~ chain alkyl
group and preferably is an alkyl group having 1 to 8 carbon atoms.
From the standpoint of the prepara-tion of the compounds of this
invention, an unsubstituted alkyl group is preferred. A
particularly preferred example of R2 is a straight chain or
branched chain alkyl group having 1 to 4 carbon atoms (for example,
a methyl group, an ethyl group, an.n-propyl group, an isopropyl
group, an n-butyl group, etc.). Suitable substituents ~Jhich can
be present on the alkyl group for R2 include, for example, an
alkoxy group, for example, a methoxy group, an ethoxy group, etc.),
a dialkylamino group (for example, a diethylamino group, etc.),
and the llke.
In the sulfamoyl group represented by the formula
-So2NR3R4 for Ql, R3 is preferably a hydrogen atom, an alkyl
group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon
- atoms). The alkyl group may be a substituted alkyl group wherein
there are 1 to 8 carbon atoms (more preferably 1 to 4 carbon
atoms) in the alkyl moiety. R4 is preferably a hydrogen atom,
an alkyl group having 1 to 8 carbon atoms (more preferably 1 to
4 carbon atoms) including a straight chain, branched chain or
cyclic alkyl group, and substituted alkyl groups having 1 to 8
carbon atoms ~more preferably 1 to 4 carbon atoms) in the alky;
moiety, an unsubstituted benzyl group, a substituted benzyl group
having 7 to 12 carbon atoms, an unsubstituted phenyl group, or
a substituted phenyl group having 6 to 9 carbon atoms. Also, R3
and R4 may be combined directly or through an oxygen atom to form
a 5- .and 6-membered.ring. The cases where: (1) R3 and R4 each
represents a hydrogen atom and (2) one of R3 and R represents a
hydrogen atom andthe other of R3 and R4 repr~sents an alkyl group
: : ,
~3~
1 having 1 to 4 carbon atoms, are particularly preEerred because of
easy availability o~ the starting materials and excellent
transferability of the dye compound formed. The same is true for
the -CoNR3R4 group. That is, R3 and R4 are preferably both
hydrogen or one is hydrogen andthe other Cl-C4 alkyl.
With respect to the -S02R5 group, R5 preferably
represents an alkyl group or a benzyl group. The alkyl may be
an unsubstituted having 1 to 8 carbon a~oms, or substituted
having 1 to 8 carbon atoms in the alkyl moiety. In particular,
an alkyl group having 1 to 4 carbon atoms and a benzyl group are
preferred because of easy availability of the starting materials
and excellent transferability of the dye compound formed. In
case of the -COOR6 group, R6 preferably represents an alkyl group,
an unsubstituted phenyl group or a substituted phenyl group
having 6 to 9 carbon atoms. The alkyl may be substituted or
unsubstituted having 1 to 8 carbon atoms (more preferably 1 to
: 4 carbon atoms) in the alkyl moiety~
Examples of suitable substituents which can be present
in the above-described substituted alkyl groups represented by
R3 to R6 include one or more of a cyano group, an alkoxy group,
a hydroxy group, a carboxy group, a sulfo group, a tetrahydro-
furyl group, a furyl group, a vinyl group, etc. Further,
examples of sui-table substituents which can be present in the
above-described substituted phenyl group represented by R4 or
R6 include one or more of a hydroxy group, a halogen atom, a
carboxy group, a sulfo group, a sulfamoyl group, an alkyl group,
an alkoxy group, etc. The number of the substituents is
preferably 1 or 2.
The above-described substituted benzyl group represented
by R can preferably have 1 or 2 substituents. Examples of
~3~8S
1 suitable substi-tuents include a hydroxy group, a halogen atom,
a carboxy group, a sulfo group, a sulfamoyl group, an alkyl
group, an alkoxy groùp, a me-thylenedioxy group, etc. In
particular, a hydroxy ~roup, an alkoxy group havin~ 1 to 4 carbon
atoms and a methylenedioxy group are pre~erred. Examples of
the substi-tuted benzyl groups include an o-, m-, or p-hydroxy-
benzyl group, an o-, m-, or p-methoxybenzyl group, a 3-hydroxy-
4-methoxybenzyl group, a 4-hydroxy-3-methoxybenzyl group,
2-hydroxy-3-methoxybenzyl group, a 2,5-dimethoxybenzyl group,
a 3,4-dimethoxybenzyl group, a methylenedioxybenzyl group, etc.
Examples of the cyclic group formed when R3 and R
combine are as follows:
i~ r~ ,~
Q 2 \ J ' -SO -N , S02-N o , etc.
As Z, a hydrogen atom is preferable. Alkyl group
represented by Z may be straight or branched and preferably
contain 1 to 8 carbon atoms, particularly preferable is an alkyl
group containing 1 to 4 carbon atoms (e.g., a methyl group, an
ethyl group, an n-propyl group, an isopropyl group, an n-butyl
2~ group, etc.).
As the substituted alkyl group represented by Z,
substituted alkyl groups wherein the alkyl moiety has 1 to 8
carbon atoms are preferable, with those having 1 to 4 carbon
atoms in the alkyl moiety being particularly preferable. As
the examples of the substituents for the substituted alkyl
groups, there are illustrated a cyano group, an alkoxy group, a
hydroxyl group, a carboxyl group, a sulfo group, etc.
As the alkylene group represented by Al or A2, those
containing 1 to 8 carbon atoms, preferably l to 4 carbon atoms,
are suitable. As the arylene group represented by Al or A2,
--10--
~3~ 5
1 those having 6 to 10 carbon a-toms are suitable. Such alkylene
or arylene group may have the substituents described for the
aforesaid R3 or R4. Above all, as the arylene group, a
phenylene group substituted by the same alkoxyalkoxy group as
foregoing R2a_0 RlaO i f bl
Y represents a moiety which releases or provides, as
a result of development processing under alkaline conditions,
an azo dye having a different diffusibility from that of the
azo dye image-providing material.
As the azo dye image-providing materials, there are
illustrated non-diffusible image-providing materials (azo dye-
releasing redox compounds) which provide a diffusible dye as a
result of self splitting due to oxidation by the` development
processing. Examples of Y effective for this type of compound
are N-substituted sulfamoyl groups. For example, there can be
illustrated as Y the group represented by the following
~ formula ~A):
(Ball)b
~ ~ (A)
``~1~
NHS02 -
In the above formula, ~ represents non-metallic atoms
necessary to complete a benzene ring, to which a carbon ring or
a hetero ring may be fused to form, for example, a naphthalene
ring, a quinoline ring, a 5,6,7,8-tetrahydronaphthalene ring,
a chroman ring, etc. Further, said benzene ring or said ring
wherein a carbon ring or hetero ring is fused to the benzene
ring may have a substituent or substituents such as a halogen
atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy
group, a nitro group, an amino group, an alkylamino group, an
:; ~
~L3~L4~5
1 arylamino group, an amido group, a cyano yroup, an alkylmercapto
~roup, a keto group, a carboalkoxy group, a hetero ring group,
etc.
~ represents an -OGl or NMG2 group, wherein G
represents a hydrogen atom or a group capable of forming a
hyaroxyl group by hydrolysis, and preferably represents a
O O
hydrogen atom, -~G3 or -C-o-G3 wherein G3 represents an alkyl
group, in particular, alkyl group having lto 18 carbon atoms
(such as a methyl group, an ethyl group, a propyl group, etc.),
a halogen-substituted alkyl group having 1 to 18 carbon atoms
(such as a chloromethyl group, a trifluoromethyl group, etc.),
a phenyl group or a substituted phenyl group, and G2 represents
a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or
a hydrolyzable group. Preferable examples o~ said hydroly2able
o
`- group represented by G2 are -CG4, -S02&5 or -SoG5, wherei.n G4
represents an alkyl group having 1 to 4 carbon atoms (such as
a methyl group); a halogen-substituted alkyl group (such as
mono-, di- or tri-chloromethyl group or a trifluoromethyl group);
an alkylcarbonyl group (such as an acetyl group); an alkoxy
group; a substituted phenyl group (such as a nitrophenyl group
or a cyanoph~nyl group); a phenyloxy group unsubstituted or
substituted by a lower alkyl group or a halogen atom; a carboxyl
group; an alkyloxycarbonyl group; an aryloxycarbonyl group; an
alkylsulfonylethoxy group; or an arylsulfonylethoxy group, and
G5 represents a substituted or unsubstituted alkyl or aryl group.
Further, b is an integer of 0, 1 or 2, and b represents
1 or 2, preferably 1, except when said ~ represents -N~G2
wherein G2 represents an alkyl group making the compound of the
~3~ 5
1 general formula (A) immobile and non-diffusible, namely, when
represen~s a group represented by -OGl or -NEIG2 wherein G
represents a hydrogen atom, an alkyl group having 1 to 8 carbon
atoms or a hydrolyzable group. Ball represents a ballast group
which will be described in detail hereinafter.
Specific examples of this type Y are described in
U.S. Published Application B351,673, U.S. Patent 3,928,312 and
Japanese Patent ~pplication (OPI) No. 50736/1978.
As other examples of Y suitable for this type of
compounds, there are illustrated the group represented by the
following formula (B):
(Ball)b
~- ~ NH-S02- (B)
In the above ~ormula, Ball, ~ and b are the same as
defined in formula (A), ~' represents the atoms necessary to form
a carbon ring, for example, a benzene ring, to which a carbon
ring or a hetero ring may further be fused to form a naphthalene
ring, a quinoline ring, a 5,6,7,8-tetrahydronaphthalene ring, a
chroman ring, etc. The above-described various rings may be
further substituted by a halogen atom, an alkyl group, an alkoxy
group, an aryl group, an aryloxy group, a nitro group, an amino
group, an alkylamino group, an arylamino group, an amido group,
a cyano group, an alkylmercapto group, a keto group, a carbo-
alkoxy group, a hetero ring or the like. Specific examples of
this type Y are described in U.S. Patents 4,055,4~8 and 4,053,312.
As the further examples of Y suitable for this type
compounds, there are illustrated the group represented by
general formula (C):
-13-
L4~35
(Ba11) b I~,NH-S2- (C)
~.
In the above formula, Ball, ~ and b are the same as
defined in formula (A), and ~" represents atoms necessary to
form a hetero ring such as a pyrazole ring, a pyridine ring, etc.,
to which a carbon ring or a hetero ring may further be fused.
The above-described rings may be substituted by the same
lQ substituents as those for the rings described in formula ~B).
Specific examples of this type Y are described in Japanese Patent
Application (OPI) No. 104343/1976.
As still Eurther examples o~ Y suitab:le- for this type
compounds, there are illustrated those represented by general
formula (D):
NH~S02-
H (D)
In the above formula, Y preferably represents a
hydrogen atom; an alkyl group, aryl group or hetero ring group
which may be unsubstituted or substituted; or -CO-G6 wherein G
represents -oG7, -S-G7 or -N ~ g (herein G7 represents a
G
hydrogen atom, an alkyl group, a cycloalkyl group or an aryl
group, which may be substituted, G8 represents the same group as
G7 or an acyl group derived from an aliphatic or aromatic
carboxylic acid or from sulfonic acid, and G9 represents a
hydrogen atom or a substituted or unsubstituted alkyl group~,
~ represents the atoms necessary for completing a fused benzene
ring which ring may have one or more substituents, and ~ and/or
-14-
.
,
.
1 the substituents on said fused benzene ring completed by ~ is a
ballast group or a ballast-containing group. Specific examples
of this type Y axe described in Japanese Patent ~pplication (OPI)
Nos. 1043~3/1976 and 46730/1978.
As still further examples o~ Y suitable for this type
compounds, there are illustrated the group represented by
general formula (E):
Ball ~ fi `~ (E)
Ç-
1 0~ ~ C ,~
G10 NHS02--
In the above formula, Ball is the same as defined in
formula (A),~ represents an oxygen atom or =N&" ~G" represents
a hydroxyl group or an amino group which may be substituted),
when ~ represents =~G", a typical example of G" is tha-t in =C=N-G"
formed by the dehydration reaction between a carbonyl reagent of
- H2N-G" and a ketone group. Examples o~ the compound of H2N-G"
- are hydroxylamines, hydrazines, semicarbazides, thiosemicarbazides,
etc. To be specific, there are illustrated, as the hydrazines,
hydrazine, phenylhydrazine, substituted phenylhydrazine having
in the phenyl moiety a substituent or substituents such as an
alkyl group, an alkoxy group, a carboalkoxy group, a halogen atom,
etc., isonicotinic acid hydrazine, etc. As the semicarbazides,-there
are illustrated, phenylsemicarbazide or substituted phenylsemi-
carbazide substituted by an alkyl group, an alkoxy group, a
carboalkoxy group, a halogen atom, etc. As the semithiocarbazides,
there are illustrated the same derivatives as with semicarbazides.
~ "' in the ~ormula represents a 5-, 6- or 7-membered
saturated or unsaturated non-aromatic hydrocarbons. To be
specific, there are illustrated, ~or example, cyclopentanone,
-15-
~3~L85
cyclohexanone, cyclohexenone, cyclopentenone, cycloheptanone,
cycloheptenone, etc.
These 5- to 7-membered non-aromatic hydrocarbon rings
may be fused to to other rinys at a suitable position to form a
fused ring system. As the other ring, various rings may be used
regardless of whether they show aromatically or not or whether
they are hydrocarbon rings or hetero rings. However, in the case
of a fused ring being formed, fused systems wherein benzene and
the above-described 5- to 7-membered non-aromatic hydrocarbon
ring are fused to each other such as indanone, benzcyclohexenone,
benzcycloheptenone, etc., are preferab;e in the present invention.
The above-described 5- to 7-membered non-aromatic
hydrocarbon rings or the above-described fused rings may have
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 alkylsulfonyl group, an arylsulfonyl
group, a halogen atom, a nitro groupr an amino group, an alkyl-
amino group, an arylamino group, an amido group, an alkylamido
group, an arylamido group, a cyano group, an alkylmercapto
group, an alkyloxycarbonyl group, etc.
Gl0 represents a hydrogen atom, or a halogen atom such
as fluorine, chlorine or bromine.
Specific examples of this type Y are described in
Japanese Patent Application (OPI) No. 3819/1978.
As the still further examples of Y for the compounds of
the present invention, there are those described in J for example,
U.S. Patents 3,443,930, 3,443,939, 3,628,952, 3,844,785 and
3,443,943.
As the different type compounds of the dye-releasing
redox compounds, there are illustrated non-diffusible dye image-
-16-
1 providing compounds which release a diffusible dye under alkaline
condition through sel~ cycli~ation or the like but, when reacted
with the oxidation product of developing agent, which do not
substantially release the dye.
As the examples of Y effec-tive for this type compounds,
~here are illustrated those represented by formula (F):
(' G13
G16 ~ (G12) _N_G14_G15 (F)
G 7 ~ G
. . q
In the above formula, ~' represents an oxidizable
nucleophilic group such as a hydroxyl group, a primary or
secondary amino group, a hydroxyamino group or a sulfonamido
group, or the precursor thereof, and preferably represents a
hydroxyl group.
: ~' represents a dialkylamino group or any of those
defined for ~', preLerably a hydroxyl group, G14 represents an
electrophilic group such as -C0~, -CS-, etc., preferably -C0-.
G15 represents an oxygen atom, a sulfur atom, a selenium atom, a
nitrogen atom, etc., and, when G15 represents a nitrogen atom, it
may be substituted by a hydrogen atom, an unsubstituted or sub-
stituted alkyl group having 1 to 10 carbon atoms, or an aromatic
compound residue having 6 to 20 carbon atoms. Pre~erably G15
is an oxygen atom. G12 represents an alkylene group containing
1 to 3 carbon atoms, and a represents 0 or 1, preferably 0. G
is a substituted or unsubstituted alkyl group containing 1 to 40
carbon atoms or a substituted or unsubstituted aryl group
containing 6 to 40 carbon atoms, preferably an alkyl group. G15,
G and G each represents a hydrogen atom, a halogen atom, a
-17-
~3~
1 carbonyl group, a sulfamyl group, a sulfonamido group, an alkyl-
oxy group containing 1 to 40 carbon atoms, or the same as
defined for G13 or, when taken together, G16 and G17 may form a
G13
5- to 7-membered ring. Also, G17 may be -(G 2) -N-G14-G 5-,
provided that at least one of G13, G16, G17 and Gl~ represents a
ballast group.
Specific examples of this type Y are described in
U.S. Patent 3,980,479.
As the examples o~ Y suitable for this type compounds,
there are further illustrated the group represented by general
formula (G): ¦ O G 9
Bal ~ C~`c~_c_N_ (G)
wherein Ball and ~' are the same as defined in formula (B), and
Gl9 represents an alkyl group (including substituted alkyl group~.
Specific examples of this type Y are described in Japanese Patent
Application (OPI) No. 35533/1978.
As the examples of Y suitable for this type compounds,
there are further illustrated the group represented by general
formula (H): G
~c,N
Ball '~C~c N' G (H)
, 11 0
~r~ ,C~C~O
wherein Ball and ~' are the same as defined in formula (B), and
Gl9 is the same as defined in formula (G). Specific examples of
this type Y are described in U.S. Patent 3,421,964 and Japanese
Patent Application (OPI) No. 4819/1977.
-18-
i95
1 As the difEerent t~pe compounds of the azo dye
image-providing compounds, there are illustrated non-diffusi~le
compounds ~dye-releasing couplers) which release a dif~usible
dye upon coupling reaction with an oxidation product of a color
developing agen~ oxidized by silver halide. As the examples of
Y effective for such compounds, the groups described in U.S.
Patent 3,227,550 are typical. For example, there are illustrated
as Y those represented by the following general formula (J):
(Ball-Coup)t-Link- (J)
wherein Coup represents a coup]er residue capable of coupling
with an oxidation product of a color developing agent, for
example, a 5-pyrazolone type coupler residue, a phenol type
coupler residue, a naphthol type coupler residue, an indanone type
coupler residue or an open chain ketomethylene coupler residue.
Ball represents a ballast group. Link represents a yroup bonded
to an active cite of Coup moiety, which bond with Coup moiety
will be split upon coupling reaction between the dye image-
providing material represented by formula (I) containing the
group represented by formula (J) as Y and an oxidation product
of a color developing agent. Examples of the Link are an azo
group, an azoxy group, -O-, -Hg-, an alkylidene group, -S-,
-S-S- or -NHSO2-,and t represents 1 or 2 when Link represents an
alkylidene group or represents 1 when Link represents other
group described above.
Of groups Y represented by formula (J), preferable
groups are those ~herein Coup represents a phenol type coupler
residue, a naphthol type coupler residue or an indanone type
coupler residue, and Link represents -NHSO2-.
As the still dif~erent type compounds of the dye
image-providing materials, there are illustrated the compounds
-19-
~3~5
1 (dye developing agent) which are initially diffusi~le under
alkaline conditions bu~, when oxidized through development
processing, become non~diffusible. Typical examples of Y
effective for this type compoun~s are those described in U.S.
~atent 2,9~3,606.
Of the above-described compounds, particularly
preferable ones are dye-releasing redox compounds and effective
~roups Y are N-substituted sulfamoyl groups. As the N-substituents
~or the N-substituted sulfamoyl groups, carbon ring groups (in
particular, o- or p-hydroxyaryl group having a ballast group
bonded thereto being preferable) or hetero ring groups are
desirable. As the examples of N-carbon ring substituted
sulfamoyl groups, those represented by formulae ~A) and (B) are
particularly preferable. As the examples of N-hetero ring
sùbstituted sulfamoyl groups, those represented by formulae (C)
and (D) are particularly preferable. As ~, the group represen-ted
by general formula (III) are particularly preferable.
OH
~ Ball
r ~ (III)
~ ~ NH-SO2-
wherein Ball represents a ballast group, T represents the carbon
atoms necessary to complete a benzene ring, which may be unsub-
stituted or substituted, or a naphthalene ring, which may be un-
substituted or substituted, the -NHSO2- group is present at -the
o- or p-position to the hydroxy group; and when T represents the
atoms necessary to complete a naphthalene ring, Ball can be
bonded to either of the two rings.
Examples of suitable substituents which can be
present on the benzene ring or the naphthalene ring include, for
example, an alkyl group (preferably an alkyl group having 1 to 7
carbon atoms), halogen atom (such as a chlorine atom, etc.), etc.
-20-
~3~ S
1 The ballast group, Ball~ is an organic ballast group
capable of rendering the dye-releasing redox compound non-
di~usible during development in an alkaline processing solu-tion
and preferably is or contains a hydrophobic residue having 8 to
32 carbon atoms. This organic ballast group can be bonaed to
the dye-releasing redox compound directly or through a linking
group, for example, an imino bond, an ether bond, a thioether
bond, a carbonamido bond, a sulfonamido bond, a ureido bond, an
ester bond, an imido bond, a carbamoyl bond, a sulfamoyl bond, etc.
Specific examples of ballast groups are illustrated
below.
An alkyl group or an al]cenyl group (for exampie, a
dodecyl group, an octadecyl group, etc.), an alkoxyalkyl group
(for example, a 3-(octyloxy)propyl group, a 3-(2-ethylundecyloxy)-
propyl group, etc., as described in Japanese ~atent Publication
No. 27563/1964, etc.), an alkylaryl group (for example, a 4-nonyl-
! ' - phenyl group, a 2,4-di-tert-butylphenyl group, etc.), an alkyl-
aryloxyalkyl group (for example~ a 2,4,-di~tert-pentylphenoxy-
methyl group, an ~ -(2,4-di-tert-phenylphenoxy)propyl group, a
l-(pentadecylphenoxy)ethyl group, etc.), an acylamidoalkyl
group (for example, a group described in U.S. Pa~ents 3,337,344
and 3,418,129, a 2-(N~butylhexadecanamido)sthyl group, etc.), an
alkoxyaryl or aryloxyaryl groùp (for example, a 4-(n-octadecyloxy)-
phenyl group, a 4-(~-n-dodecylphenyloxy)phenyl group, etc.), a
residue containing both an alkyl or alkenyl long-chain aliphatic
group and a water-solubilizing group such as a carboxy group or
a sulfo group (for example, a l-carboxymethyl-2-nonadecenyl
group, a l-sulfoheptadecyl group, etc), an alkyl group substituted
with an ester group (for example, a l-ethoxycarbonylheptadecyl
group, a 2 (n-dodecyloxycarbonyl)ethyl group etc.), an alkyl
s
1 ~roup substi~uted with an aryl yroup or a he-terocyclic group
(for example, a 2-[~-(3-me-thoxycarbonylheneicosanamido)phenyl]-
ethyl group, a 2-[~-~2-n-octadecylsuccinimido)phenyl]ethyl group,
etc.), and an aryl group substituted with an aryloxyalkoxycarbonyl
group (for example, a 4-[2-(2,4-di-tert-pentylphenoxy)-2-methyl-
propyloxycarbonyl]phenyl group, etc.).
Of the above-described organic ballast groups, those
bonded to a bridging group as represented by the following
general formulae (IV) to (VII) are particularly preferred.
-CoNH-R7_o ~ (IV)
(R8)n
--CoNH-R7-o--R (V)
O R10 (VI)
-CONHR (VII)
wherein R represents an alkylene group having 1 to 10 carbon
; atoms, preferably 1 to 6 carbon atoms (such as a propylene
group, a butylene group, etc.); R8 represents a hydrogen atom
or an alkyl group having 1 to 10 carbon atoms, preferably 1 to
6 carbon atoms (such as a tert-amyl group, etc.); n represents
an integer o~ 1 to 5 (preferably 1 to 2); R9 represents an alkyl
group having 4 to 30 carbon atoms, preferably 10 to 20 carbon
atoms (such as a dodecyl group, a tetradecyl group, a hexadecyl
group, etc.); and R10 represents an alkyl group having 8 to 30
carbon atoms, preferably 10 to 20 carbon atoms (such as a hexa-
decyl group, an octadecyl group, etc., or a substituted alkyl
group having 8 or more carbon atams in which the alkyl moi~ty has
one or more carbon atoms, with examples of suitable substituents
being one or more of, for example, a carbamoyl group, etc.
Specific examples of the sulfamoyl groups represented
by the formula (III) are illustrated below:
~ -
- ,
~L13~4~5
OH
~ NHS02-
CH 3 ~/
Cl 6 3 3 (n )
OH
~ NHS02-
3~
( 2 ) 2 ~3 5 11
C5Hll t
OH
~NHS02 -
CH~
O-fHcoNHcl6H33 (n)
CH3
OH
~ NHSO2-
OCHCH2-
C15H31 (n)
OH
C~ NHS02-
CH3~
OC16H33 (n)
--23--
~L~L3~5
1 OH
----b 2
~,l~
18H37(iSo)
OH
~NHS02 -
) C16H33
CH
OH
,[~NHS02 -
( ) 18 37 C'H
OE~
~ NHS02-
CH 3~f J
O-CH2CH-~
C2H5 15 31 (
OH
NHSO2
O-CHCONH(CH2)30- ~ C5~11(t)
CH
C5Hll(t)
-24-
- i : . . .
~3~5
OH
C5Hll (t) ~NHS02-
5 11~ OCH2CH20~-~
CH3
OH
~\~ NHS02 -
5 11~ (CH2 ) 3NHCOCH--O~
105 11 (t) C 3 CH3
C5Hll t
~, CONH ( CH2 ) 3-- ~3C5Hll -t
NHS02 -
CH2CH3
20~rCoNH-cH-o~csHll-t
NHS02--
.
~CNH--(CH2 ) 40~tC5Hll--t
3 O NHS02-
--25--
1~3~
cNHcH2c3o ~CS~ t
NHS02--
OH 1
~, CNH ( CH2 ) 4 0
NHS02 -
~1' S21~H(C~I2~,~1~15~31
NHS 2 -
OH
H31C15'~
~C01~3~
14 H29
NHS02--
OH
CONHCl8El37
NHS02--
~ .
--26--
33L48~
i~\ ,/1" ~'CNHC~12C-
NHS02 -
(CH2 ) 4-O -~ C5Hll-t
NE~SO2-- 5 11
OH
~' CO(CH2)1'LCH3
NHS02--
OH
H31C15~3~
NHSO2--
OH COOCl 4H2 9 (n )
~,q, CONH~
~/ C.
NHS02 -
OH ~ CH2CH2CN
(n)
N 2
OH NHCOCH-O~ 9C5Hll (t)
[~CONH ~ C2HS C5Hll (t)
3 O NHS02--
--27--
~319L~
1 ~urthermore, the groups described in Research Disclosure,
Vol. 130, No. 13024 (February, 1975) are useful for Y.
A preferred compound according to the present invention
is a compound represented by the above-described general formula
(I) or ~II), and in which Rl represents a -CH2CH2- group; R
and R2b, which may be the same or different, each represents a
straight chain or branched chain alkyl group having 1 to 4 carbon
atoms (for example, a methyl group, an ethyl group, an n-propyl
group, an isopropyl group, an n-butyl group, etc.).
Ql represents a hydrogen atom or a sulfamoyl group
represented by the formula -So2NR3R4, wherein R3 and R4, which
may be the same or different, each represents a hydrogen atom,
an alkyl group including unsubstituted alkyl groups having 1 to
4 carbon atoms and substituted alkyl groups having 1 to 4 carbon
atoms in the alkyl moiety, with examples of suitable substituents
n the substituted alkyl group including a cyano group, an
alko~y group, a hydroxy group, a carboxy group, a sulfo group,
etc., and also R3 and R4 can combine directly or through an oxygen
ato~n to form a 5- or 6-membered ring.
Q2 represents a hydroxy group or an -NHSO2R a group
substituted at the 5-position, wherein R4a has the same meaning
as R~ defined im~ediately above except R4a cannot be a hydrogen
atom; and Y represents a sulfamoyl group represented by the
general formula (III).
A particularly preferred compound according to the
present invention is a compound represented by the above-
described general formula ~I), and in which Rla represents a
-CH2CH2- ~roup; R2a represents a straight chain or branched chain
alkyl group having 1 to 4 carbon atoms.
Q represents a hydrogen atom or a sulfamoyl group
-28-
~3.~8S
1 represented by the formula So2NR3~4, where;n R3 and R4, which
may be the same or dif~erent, each represents a hydrogen atom,
an unsubstituted alkyl group haviny 1 to 4 carbon atoms or a
substituted alkyl group having 1 to 4 carbon atoms in -the alkyl
moiety, with examples of suitable substi-tuents for the substituted
alkyl group for R3 and R4 including a cyano group, an alkoxy
group, a hydroxy group, a carboxy group, a sulfo group, etc., and
also R3 and R4 can combine directly or through an oxygen atom to
form a 5- or 6-membered ring.
Q2 represents a hydroxy group or an -NHSO2R group,
wherein R4a has the same meaning as R4 defined immediately above
except R4a cannot be a hydrogen atom, at -the 5-position.
Y represents an o-hydroxyphenylsulfamoyl group having
an alkyl group at the meta position to the hydroxy group in
addition to a ballast group.
Specific examples of dye image-providing material
according to the present invention are illustrated below. How-
ever, the present invention should not be construed as being
limited to these specific examples.
Compound 1
OH ICH3
~ ~ S02NH-C-CH3
CH3SO2NH N=N ~ OCH2CH20R
OH
S02NH ~
` CH3
~)C16H33-n
wherein R is CH3
-29-
, ' ' ' ~ ~
~31~35
Compound 2
Same compound as Compound 1 except for R2 ls C2H5.
Compound 3
OH ~
~ S02N ¦
CH SO H ` ~ `OCH2CH20CH3
\ OH
S2 NH~
~ C~3
Cl 6H3 3-n
Compound 4
OH
~ 502N}I--R
CH3SO2NH N= ~ 2 2 C 3
~ 0~ .
SO2NH ~
CH3
OC16H33-n
~herein R is H
Compound 5
Same compound as Compound 4 except for R3 is CH3.
Compound 6
Same compound as Compound 4 except for R3 is n-C4Hg.
-30-
, . : ~ .
~3~8~
Compound 7
. OHICH3
, S 02NH -C -CH
CH3SO2- H ~ O-cH2cH2-o-R
OH
S02NH ~
O-CE12CH20-~ C5~Ill--t
wherein R is CH3
Compound 8_
Same compound as Compound 7 except for R is C2H5.
Compound 9
OH CH3
2NH I C 3
CH3SO2NH N=N ~ OCH2CH2-o-R2
\ SO2NH ~H
2 ~ CH3
wherein R is CH
18 37 n
Compound 10
Same compound as Compound 9 except for R? is C2H5.
:: ~, .,
1 mpound 11
OHCH3
~ 2 f 3
3 2 ~ OCH2CH20CH3
OH
S2NH~
~CH 3 C~--t
0CH2CONH(CH2)3-0~C5 11
Compound 12
OH I 3
~ 50 NH-C-C3 2 C5 11
CH3S02NH N=N~ ~ OCH2CH20R ~ ~
2 ~ CONH(CH2)3-0 ~ 5 11
wherein R is CH3
Comp.ound 13
Same compound as Compound 12 except for R2 is C2H5.
-32-
~3~
1 Compound 1~
OEI
~X~ S02~
CH3S02NH N=N ~ ~ OCH2CH20CH3 C~-t
--~ ~ONH ( CH3 ) 3-O~ C 5Hll -t
S02NH~ OH
Compound 15
1 t)
IOH 3
S02NH-R
~J~ C5Hll-t
CH3so2NH N N~ OCH2CH20CH3 ~
\=~ CONH (CH2 ) 3-O~ ~ C5Hll
S02NH y \~ OH
. ~ :
wherein R3 is H
Compound 16
Same compound as Compound 15 except for R is CH3.
Compound 17
Same compound as Compound 15 except for R is n-C4H9
Compound 18 OH I 3 ,
~, S02NH-C--CH3
CH3S02NH N=N~-OCH2CH20R
S02NH-~- OCH2cH2ocH3
OH
S02NH
wherein R2 is CH3 ~CH3
Cl ~;H33-n
--33-
~.~3~48S
~ Compound 19
-
Same compound as Compound 18 except for R2 is C2H5.
Compound 20
1ll r--
~ S02N
CH3S02NH N=N4;~-oCH2CH2oCH3
S02NH - e ~ -OCH2CH20CH3
OH
SO2NH ~
CH3
OC16H33-n
Compound 21
OH
~ 502NIl-R
CH3S~2 H N N ~ ~-OCH2CH20CH3
SO2NH ~ -OCH2CH20CH3
OH
SO NH
11
~ CH3
wherein R is H OC16H33-n
Compound 22
Same compound as Compound 21 except for R3 is OEI3.
Compound 23
. .
Same compound as Compound 21 except for R is n-C~H5.
-34-
~13~
1 Compound 24
OH I 3
~ ,SO2NH-I-CH3
CH3S2~NH N=N ~ \~ C~I2cH2cH3
S02NH~ ~ OCH2CH20CH3 5~11
\ ~ &ONH(CHz)3-o ~ 3 C5Hll-~
S02-NE~ OH
~
Compound 25
Same compound as Compound 4 except for R3 is C2H5-.
Compound 26
Same compound as Compound 4 except for R3 is CH3OCH2CH2-.
Compound 27
Same compound as Compound 4 except for R3 is -CH(CH3)2.
Compound 28
.
OH
~ ~ 02N(CH3)2
CH3S02NH N=N~ CH2cH2cH3
S02NH~
CH3
16 33
-35-
Compound 2 9
_
OH
~,?f ~ S02N (C2H5) 2
3 2 ~>- OCEI2CH20CEI3
OH
S02NH ,~
CH3
Cl6H33-n
10 Compound 30
OH R3
~ S2N~ R4
CH3S02 H N=N~ OH
S02NH
~CH3
C16 33(n)
wherein R is H and R is cyclopentyl
Compound 31
Same compound as Compound 30 excep-~ for R3 is H and
R is cyclohexyl.
Compound 32
Same compound as Compound 30 except for R3 is H and
R is - l
CH2~ o J
Compound 3 3
Same compound as Compound 30 except for R3 is H and
R4 is-CH2 ~ 3
~ J
OCH3
-36-
~3~5
7 Compound 34
. . .
Same compound as Compound 30 except for R3 is H and
R is -CH -CH=CH ~
Compound 35 CH
IOH I 3
~ 02NH-C-CH3
~ CH3
CH3S02NH N=N~QCH2CH20R2
O2NH ~ OCH3
(~)-C18H37NHCOJ~` N
wherein R is CH3
Compound 36
Same compound as Compound 35 except for R2 is C2E~5.
Compound 37
. . .
OH
~ S02N
CH3SO2NH N= ~ OCH2CH2OCH3
2 ~ OCH3
(n)-C18H37NH C ~ N ~
H
Compound 38
OH
~- 502NH-~
CH3SO2 H N=N ~ -OCH2CH2OCH3
SO2N ~ ~ 3
(n) Cl~H37NH CO
wherein R -is H
-37-
~3~5
1 Compound 39
Same compound as Compound 38 except for R3 is CH3.
Compound 40
Same compound as Compound 38 except for R is (n)-C4Hg.
Compound 41
pH fH3
~ CH3
3 2 N=N ~ OCH2CH20-CH3
1 0 ~502NH,~_ N~I2
. C15H31 ~n)
Compound 42
IOH I 3
~\~ So2NH-c-cH
CH3SO2NH N=N ~ OCH2CH20CH3
02NH ~ 12 25 ( )
~O Compound 43
OH I 3
~ SO2NH-l_CH3
CH3S02NH N=N~- OCH2cH2ocH3
S02NH ~ NH-C12H25-(n)
6_~
-38-
.
,
~3~L~8~
1 Compound 44
OH CH3
~J 2 ; 3
CH3S2NH N N ~ 2 2 3
O-COCH
SO NH I 3
2 ~ ~
16 33 ( )
Com ound 45
OH fH3
~ SO2NH-C-CH3 5 11 t.)
CH3SO2NH N=N~ ~ OCH2CEI20CH3 ~
CONH(CH2)30 ~ 5 11 ( )
SO2NH~/ ; OCOCH3
Compound 46
-
OH 7 3
2NH-f-CH3
~ CH3 C5~11-(t)
CH3S02NH N=h4~0CH2cH20cH3 ` ~\
CONH(CH2)30 ~ C5Hll-(t)
S02NH~ O-CO-COOC2H5 ~ :
/~<
W
-39-
1 Compound 47
OH ~ R3
~ ~ 2 ~ R4
CH3S02NH N--N ~ ~-OCH2CH20cH3
S2NH 17 35 ( )
\~ .
SO3H
wherein R3 and R are CH3
Compound 48
Same compound as Compound 47 except for R3 and R4
2 5
Compound 49 C,H3
OH
,S02NH-C-CH3
3 02NH /~
~ ~ 2 20C 3 /y ~
~ SO NH NHCO~ ~ ~ C5Hll-(t)
HO~N~N NHCOCH20~ C~,--tt3
ce~C~ -
~ '
Compound 50 -OH
I CH3
S02NH-~-CH3
CH3S02NH N=~OCH2CH20CH3
2 ~ ~ _NHCocl2H25-(n)
-4~-
,~
::
1~3~L~85
1 Compound 51
OH CH3
~ CH3
CH3SO2NH N=N. ~ 2 2 C 3
~ OH
S02NH ~CH2CH2 ~
.10 OH
Compound 52
O~ CH3
[~ S02NH--C-CH3
CH3S02NH N=N~ OCH2CH20CH3
- , S02NH_Q OCH2CH20CH3
SO2NH ~ ~ OCH3
(n)-cl8H37NH CO N
The preferred dye-releasing redox compound according to
the present invention releases a novel magenta dye compound
represented by the following formula (VIII) or (IX):
OH
~ (VIII) .
Q2 N=N~ o-Rla_O_R2a
\=< S02NH2
-41-
- . -:;
- .
~3~4~35
1 OH
Q ~ O R1a ~ R2a (IX)
S02NH ~ o_Rlb_o_R2b
2 2
wherein Ql, Q2~ Rl and R2 each has the same meaning as de~ined
in the general formula (I) or (II), when the compound is
o~idized under alkaline conditions.
The preferred compound according to the present
invention can be ob-tained by a condensation reaction of a
sulfonyl halide represented by the formula (X) with an amine
represented by the formula (XI) or (XII):
OH
Q ~ ~ o_R1a_O_R2a (X)
O S02X
OH
Ball (XI)
T ~
~NH2
H2N- ~ o-Rlb-o-R2b (XII)
-~12-
~, :
1 wherein Ql, Q2, ~1, R2 and Y each has the same meaning as defined
in the formula (I) or tII); T and sall each has the same
meaning as defined in the formula (ILI); and X represents a
halogen atom (for example, a chlorine atom, a fluorine atom,
etc.). The other compounds of the present invention can be
easily prepared by methods analogous to that set forth below.
In general, the condensation reaction is preferably
carried out in the presence of a basic compound at about -20
to about ~00C, preferably about 0C to about 100C, more
preferably 0 to 50C. Examples of suitable basic compounds
which can be employed include a hydroxide of an alkali metal or
an a~kaline earth metal (for example, sodium hydroxide, potassium
hydroxide, barium hydroxide, calcium hydroxide, etc.), an
aliphatic amine (for example, triethylamine, etc.), an aromatic
amine (for example, N,N-diethylamine, etc.), a heteroaromatic
amine (for example, pyridine, quinoline, ~ -, ~-, or ~-picoline,
lutidine, collidine, 4-(N,N-dimethylamino)-pyridine, etc.), or a
heterocyclic base (for example, 1,5-diazabicyclo~4,3,0]nonene-5,
1,8-diazabicyclo[5,4,0]undecene-7, etc.). A heteroaromatic
amine is particularly preferred of the above-described basic
compounds where a compound represented by the formula (X)
wherein X is a chlorine atom, that is, a sulfonyl chloride is
used. Suitable solvents ~or the reaction are: ketonic solvents
(e.g., acetone, methyl ethyl ketone, etc.), ethereal solvents
(e.g., diethyl ether, tetrahydrofuran, dioxane, l,~-diethoxy-
ethane, diethyleneglycol dimethyl ether, 1,3-dioxolane, etc.~,
amides solvents (e.g., N,N-dimethylformamide, N,N,-dimethyl-
acetamide, N-methylpyrrolidone, etc.), haloalkanes (e.g.,
chloroform, dichloromethane, 1,2-dlchloroethane, etc.) and so on.
A diazo component represented by the formula (XV)below
which is required for the preparation of the compound represented
by the formula (X) can be synthesized in the following manner:
-43-
~3~L4~5
Na~ ~O-Rl-O-R2
S03Na
(XIII)
2 ~ O-R -O~R Reduction 2 ~ -O-Rl-o-R2
SO3Na SO3~I
(XIV) (XV)
wherein Rl and R2 each has the same meaning as defined in the
1~ formula (I) or (II).
The first step is a reaction of a compound of the
formula (XIII)(sold by Hoechst Aktien~esellschaft) with an
R2-O-Rl-O moiety. The latter is obtained by treating an alcohol
of the formula R2-O-R1-OH with metallic sodium or sodium hydride.
The reaction for obtaining a compound of the formula (XIV) is
preferably carried out using an excess amount of the alcohol of
the formula R2-O-Rl-OH as a solvent. The alkoxide of the formula
R2-O-Rl-ONa is used in an amount of from about 1 mol to about
50 mol, preferably from about 1 mol to about 10 mol, and more
preferably, from about 1 mol to about 3 mol, per mol of the
compound having the formula (XIII). A suitable reaction
temperature ranges from about -20C to about 150C, preferably
from 0C to 100C, and more preferably from 30C to 85C, in
order to control the formation of by-products. The compound
represented by the general formula tXIII) and the alcohol used
in this synthesis are also commercially available compounds.
Another method for obtaining a compound of the
formula (XIV) is to suspend a compound of the formula (XIII) in
an alcohol of the formula R2-O-Rl-OH which is used as a solvent,
and to react with sodium hydroxide in the presence of manganese
~3~
1 dio~ide or sodium silica-te (Na2O nSiO2 wherein n i5 about 1 to
about 3). More particularly, 1 mol of a compound of the
formula (XIII) and from abou-t 10 g to about 1 kg, preferably
from about 10 g to about 500 g, more preEerably ~rom abou-t 30 g
to about 100 g, of manganese dio~ide are suspended in from
about 100 m~ to abou~ 50 ~, preferably from about 300 m~ to
about 5~,, more preferably from about 400 m ~ to about 2~, of
an alcohol having the formula R2-O-Rl-OH and then treated with
from about 1 mol to about 50 mol, preferably from about 1 mol to
about 10 mol, more pre~erably from about 1 mol to about 3 mQl,
of sodium hydroxide. In this method, a pre~erred reaction
temperature ranges from about 0C to about 150C, more preferably
from 0C to 100C, most pre~erably from 30C to 85C. This
method is preferred over the former since an inflammable material
such as metallic sodium or sodium hydride is not used.
Preferable compounds represented by general formula
(XV) are those wherein Rl represents -CH2CH2- and R2 represents
a straight or branched chain alkyl group having 1 to 4 carbon
atoms. More preferable compounds are those wherein Rl in the
general formula represents -CH2CH2- and R represents a straight
alkyl group having 1 to 4 carbon atoms. Still more preferable
compounds are those wherein Rl in -the general formula represents
-CH2CH2- and R2 represents a methyl group or an ethyl group.
Specific examples of the compounds represented by
general formula (XV) are illustrated below.
Compound ~XVa)
2 2 CH3
~ so3
NH2
-45-
- ' ., '' .
~13~ 5
1 Compound (XVb)
_ _
2 2 2 5
S03H
NH2
Compound (XVc)
O-CH CH -O-C H -n
~ So2H
NH2
Compound (XVd)
.
O-CH2CH -O-C4H -n
503~
NH2
~0
As the methods for redueing the nitro group of the
eompounds represented by general formula (XIV) to obtain compounds
(I), reduction with iron dust, catalytie hydrogenation (Raney
niekel or palladium-earbon catalyst), and hydrazine reduction
(Raney nickel, palladium-carbon or active carbon catalyst) are
typical. Other methods for reducing the nitro groups to the :
amino group are described in, for example, R. ~. Wagner et
H. D. Zook, Synthetic Organie Chemistryr Chap. 24, pp 654-657
(John Wiley, New York (1953)), S.R. Sandler et W. Karor Organic
Funetional Group Preparations r Chap. 13, pp. 339-345 (Academie
-46-
~L:3L3~L85
1 Press, London, (1968i), and the like. These methods are also
effective for synthesizing compounds of general formula (XV).
The me~hod for reducing the nitro group o~ the
compound represented by formula (XIV) to obtain compound (XV)
will be described in more detail taking the method of reducing
with iron dust for instance. About 1 mol to about 100 mols,
preferably about 1 mol to abou-t 50 mols, more preferably about
1 mol to about 10 mols, of iron dust (commercially available
reduced iron or the like being preferable) is used per 1 mol of
the compound represented by general formula (XIV). As the
solvent for the reduction reaction, water and alcohols (e.g.,
methanol, ethanol, methoxyethanol, etc.) are preferable. It is
also possible to use these solvents in combination. Further,
ammonium chloride is desirably added as a reaction initiator in
a slight amount (about 1/100 to about 1/10, preferably about
1/100 to about 1/20, of the weight of the compound of general
formula (XIV)). The temperature of the above-described reaction
is desirably maintained at about 30~C to about 150C, preferably
about 50C to about 100C. The thus obtained reaction solution
is filtered to remove insolubles and, upon pouring the filtrate
into a poor solvent (e.g., isopropyl alcohol), sodium salt of
the compound of general formula (XV) is precipitated. Also, when
the filtered reaction solution described above is neutralized
with conc. hydrochloric acid, there can be obtained the compound
of general formula (XV~ as an inner salt.
An azo dye represented by the formula (XVII) below can
be obtained by diazotizing a diazo component represented by
the formula (XV) and coupling it wi-th a compound represented by
the formula (XVI), i.e., a coupler or a coupling component.
(The coupler component is described in, for example, U.S. Pa~ent
3,954,476.)
~3~ 5
1 Diazoti~ation of compound (XV) can be conducted
according to the methods described in, for example, Yutaka
Hosoya, S]~in Senryo Kagaku (Ney Dye Chemistry), (Gihodo, (1963)),
pp. 114-120, or Hiroshi Horiguchi, Sosetsu Gosei Senryo (Revie~J
on Synthetic Dyes), (Sankyo Shuppan (]970)), pp. 114-124. Above
all, it is preferable to diazotize diazo component (XV) according
to a method usually called the reversal method. In this method,
1 mol of diazo component (XV), about 1 mol of sodium nitrite and
about 1 mol of sodium hydroxide (or hydroxide of other alkali or
alkaline ear~ metal) are dissolved in water, and this mixture is
added to a cooled mineral acid aqueous solution (e.g., dilute
hydrochloric acid, dilute sulfuric acid, etc.). As the amounts of
sodium nitrite and sodium hydroxide,the above-described amounts are
preferable, though they may be added in excess amounts. The thus
obtained solution of diazonium salt is mixed with an aqueous solvent
solution or aqueous solution containing about 1 mol of the coupler
of general formula (XVI) to conduct the coupling reaction. As
the organic solvents for dissolving the coupler, water-miscible
solvents are preferable. For example, alcohols (e.g., methanol,
ethanol, ~-propanol, methoxyethanol, ethoxyethanol, etc.),
carbonamides (e.g., N,N-dimethylacetamide, N,N-dimethyl formamide,
etc.), carboxylic acids (e.g., acetic acid, propionic acid, etc.)
are preferable. It is also possible to dissolve the coupler of
general formula (XVI) in the mixture of these solventsO Further,
the coupler of general formula (XVI) may be used as an alkaline
aqueous solution. Upon this coupling reaction, it is preferable
to allow a basic material to coexist. As the preferable basic
material, there are illustrated sodium acetate, potassium acetate,
sodium hydroxide, potassium hydroxide, sodium carbonate, potassium
carbonate, sodium hydrogencarbonate, etc. Details of the
-48-
~3~85
1 coupling reaction will be described hereinafter. Descriptions
of the foregoing I~origuchi's book, pp. 124-129, H. E. Fierz-
David et L. slangy~ Fundamental Process of Dye Chemistry,
(Interscience Publishers IncO, New york (1949)), pp. 239-297,
and K. Venkataraman, The Chemistry of Synthetic Dyes (Academic
Press Inc., New York (1952)), Chap. 11 are also instructive.
A compound represented by the formula (X) is prepared
by converting the sulfonic acid group of the azo dye to a
sulonyl halide using a halogenating agent.
10 Summari~ing: OH
z ~ ~ Diazotized
Q Q N=N - ~ o-Rla-o-R2a
(XVI) S03H
(XVII)
Chlorinatin~ Agent ~ (X)
,~
~herein Q , Q , R and R2a each has the same meaning as defined
in the formula (I) or (II).
In order to convert the compound of the formula (XVII)
to a compound of the formula (X), a chlorinating agent sùch as
phosphorus oxychloride (POC~3), thionyl chloride (SOC ~) or
phosphorus pentachloride (PC~5) is preferably used. The
chlorination reaction is preferably carried out in the presence
of an N,N-di-substituted carbonamide such as N,N-dimethyl-
acetamide, N,N-dimethylformamide, N-methylpyrrolidone, etc.,
as a catalyst.
In particular, compounds wherein X represents chlorine
are preferable. Synthesis of such compounds will now be
described. As the chlorinating agent for converting a sulfonic
acid group in general formula (XVII) to chlorosulfonyl group,
-49-
1 there are illustra-ted the agen-ts above-described. This reaction
proceeds smoothly in the presence of a carboxylic acid amide such
as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-
pyrrolidone, etc. The necessary amount oE the above-described
chlorinating agent is a stoichiometric amount but, in many cases,
it is desirable to use it in excess (1.5 to 50 times, preferably
1.5 to 10 times the theoretical amount). In most cases, this
reaction proceeds at room temperature (about 25C). Where the
reaction is too vigorous, it is possible to cool it to about
0C. On the other hand, where the reaction proceeds too slowly,
the reaction system may be hea-ted within the range of 25C to
150~C (preferably 25~ to 100C).
Compounds wherein X represents other halogen can also
be synthesized according to the method described in Houben-Weyls
Methoden der Or_anishen Chemie, edited by E. M~ller, Vol. IX,
pp. 557-598 (1958).
. . Typical examples of the amine represented by the
formula (XI) are described, for example, in U.S. Patents
4,055,428, 3,932,380 and 3,931,144 and Research Disclosure, Vol.
_ . _
130, No. 13024.
A typical method for the preparation of the amine
represented by the formula (XII) is schematically illustrated
below:
(XIV) ~ O N - ~ ~ O-R -O-R + Compound (XI)
S02C
(XVIII)
Condensation ~ 1 2
Reaction ~ O2N - ~ O-R -O-R Reduction
y
(XIX)
-50-
.
~13~
H 2N ~ - O-Rl -O-R
y
(XII)
wherein Rl, R2 and Y each has the same meaning as defined in the
formula (II).
In order to obtain a compouncl represented by the formula
(XVIII) from a compound represented by the formula (XIV), a
chlorinating agent such as those described in the preparation
of the compound of the formula (X) described above can be used.
In this case, the reaction is preferably carried out in the
presence of an N,N-di-substituted carbon amide.
The condensation reaction of the sulfonyl chloride
represented by the formula (XVIII) and an o- or p-hydroxyaryl-
amine having a ballast group bonded thereto represented by the
formula (XI) to obtain a compound of the formula (XIX) is
preferably carried out in the presence of a basic compound, with
suitable examples of basic compounds being as described with
respect to the reaction of the compound of the formula (X) with
the compound of the formula (XI) or (XII).
Typical examples of reduction reactions for obtaining
a compound represented by the formula (XII) include a catalytic
hydrogenation (e.g., using Raney nickel, palladium-carbon or
charcoal as a catalyst), a reduction with iron powder, a reduction
with hydrazine, etc. It should be emphasized that, in the
compound of the formula (XII), the basicity of the amino group
is increased due to the presence of the R2b-O~Rlb-0- group.
Accordingly, the following condensation reaction of the compound
of the formula (XII) with a sulfonyl halide of the formula (X)
proceeds easily.
~3~5
Typical synthesis examples oE the dye-releasiny
redox compounds used in the present inven-tion and in-termedia-tes.
SYNT~IESIS EXAMPLE 1
Synthesis of Sodium 2-t2-Methox~ethoxy)-5-nitrobenzenesul~onate
. . .
[Method 1]
To a solution of sodium 2-methoxyethylate prepared by
adding 7.3 g of sodium hydride (14.6 g of a 50~ su~pension in
liquid paraffin) to 330 m.'' of methyl Cellosolve, was added 55 g
of sodium 2-chloro-5-nitrobenzenesulfonate with stirring. The
reaction mixture was heated at 80 to 85C on a water bath with
stirring for 30 minutes. A~ter filtering the mixture while hot,
1.5 liters of isopropyl alcohol was added to the filtrate. The
crystals thus-precipitated were recovered by filtration and
washed with 109 mQ of isopropyl alcohol.
Yield: 59 g; Melting Point: 238 to 239C
[Method 2]
. . _.. = _
: A mixture of 5.2 g of sodium 2-chloro-5-nitrobenzene-
sulfonate, 0.6 g of manganese dioxide, 15 m~ of methyl Cellosolve,
1 m~ of water and 0.95 g o~ sodium hydroxide was stirred at 75C
for 40 minutes. After cooling, the insoluble materials were
removed by filtration and the filtrate was poured into 100 m~ of
isopropyl alcohol. The crystals thus-precipitated were recovered
by filtration to obtain 4.8 g of sodium 2-(2-methoxyethoxy)-5-
nitrobenzenesulfonate. Melting Point: 238 to 239C
[Method 3]
Using the same procedure as described in Method 2 above
except that 0.8 g of sodium silicate (No. 3, Na20 n SiO2 wherein
n is about 3) was used in place of the manganese dioxide, 4.8 g
of sodium 2-(2-methoxyethoxy)-5-nitrobenzenesulfonate was
obtained. Similar results were obtained using Na20 n SiO2
wherein n is about 1, about 2 and about 2.5, respec-tively.
-52-
:~3~4~5
SYNTHESIS_E AMPLE 2
Synthesis of Sodium 2-(2-Ethoxyethoxy)-5-~itrobenzenesulfona-te
I'o a solution of sodium 2-e-thoxye-thylate prepared by
adding 7.3 g of sodium hydride (14.6 g of a 50% suspension in
liquid paraffin) to 300 m~ of e-thyl Cellosolve was added 55 g
of sodium 2-chloro-5-nitrobenzenesulfonate. Ihe reaction mixture
was heated at 80 to 85C with stirring for 30 minutes. After
completion of the reaction, the insoluble materials were removed
by fil-tration and from the filtrate 150 m~ of ethyl Cellosolve
was distilled off under reduced pressure. To the concentrated
solution was added 300 m;~ of isopropyl alcohol and the mixture
was cooled with ice. The crystals which thus precipitated were
recovered by filtration, wa~ched with 100 mQ of isopropyl alcohol
and air-dried. Yield- 33 g; Melting Point: 248 to 249C
SYNTHESIS EXAMPLE 3
Synthesis of Sodium 2-(2-Butoxyethoxy)-5-nitrobenzenesulfonate
The above compound was obtained in the same manner as
described in Method 2 of Synthesis Example 1 except that ethylene
glycol monobutyl ether was used in place of the methyl Cellosolve.
Melting Point: 104 to 106C
SYNTHESIS EXAMPI,E 4-1
Synthesis of Sodium 5-Amino-2-~2-methoxyethoxy)benzenesulfonate
. _ _ .. ..
A mixture solution of 30 g of soclium 2-(2-methoxy-
ethoxy)-5-nitrobenzenesulfonate, 30 g of reduced iron, 0.6 g of
ammonium chloride and 60 m~ of ~ater was heated at 80 to 85C
with stirring for 2 hours. After completion of the reac-tion,
the insoluble materials were removed by filtration, 200 m~ of
isopropyi alcohol was added to the filtrate and the mixture was
cooled with ice. The crystals thus precipitated were collected
by filtration, washed with 50 m~ of isopropyl alcohol and air-
dried. Yield: 23 g; Melting Poin-t: above 250C
-53-
1131~BS
SYNTMES I S EXAMPLE 4 - 2
Synthesis of Compound (XVa)
. .
A mixture solution oE 20 g of sodium 2-(2-methoxy-
ethoxy)-5-nitroben~enesulfonate ob-tained in Synthesis Example 1,
10 g of reduced iron, 0.4 y of ammonium chloride, 40 m~ of
isopropyl alcohol and 40 mP of water was stirred for 90 minutes
at 77C. After completion of the reaction, insolubles were
removed by filtration, and 20 m-~ of conc. hydrochloric acid (36%)
was added to the filtrate. Crystals thus formed were collected
by filtration, washed with 50 mQ of isopropyl alcohol, and air-
dried. Yield: 19.6 g; Melting Point: 286-289C
Elemental Analysis
H C N
9 15N6S (%): 5.70 40.74 5.28
(monohydrate)
Found (%): 5.50 41.02 5.18
SYNTHESIS EXAMPLE 4-3
Synthesis of Compound (XVb)
A mixed solution of 10 g of sodium 2-(2-ethoxyethoxy)-
5-nitrobenzenesulfonate obtained in Synthesis Example 2, 5 g of
reduced iron, 0.2 g of ammonium chloride, 20 m~ of isopropyl
alcohol and 20 md of water was stirred for 2 hours at 77C. ~fter
completion of the reaction, insolubles were removed by filtration,
and 10 m~ of conc. hydrochloric acid (36%) was added to the
filtrate. Crystals thus formed were collected by filtra-tion,
washed with 30 m~ of isopropyl alcohol, and air-dried. Yield:
7.6 g; Melting Point: 278-283C
Elemental Analysis
H C N
lOH15 O5S (~): 5.79 45.97 5.36
Found (~): 5.73 45.86 5.24
-54-
~ .
485
1 SYNTHESIS EXAMPLE 4-4
Synthesis ot Compound (XVc)
A mixture solu-tion o~ 10 g o~ sodium 2-(2-propoxy-
ethoxy)-5-nitrobenzenesulfonate, 5 g of reduced iron, 0.2 g of
ammonium chloride, 20 m~n of isopropyl alcohol and 20 ml' of water
was stirred at 77C for 2 hours. After completion of the
reaction, insolubles were removed by filtration, and 10 m~ of
conc. hydrochloric acid (36%) was added to -the filtrate. Crystals
thus formed were collected by filtration, and air-dried. Yield:
7.1 g; Melting Point: 287-290C
Elemental Analysis
H C - N
11 17 5 (%) 6.22 47.99 5.09
Found (%) 6.11 47.41 4.99
SYNTHESIS EXAMPLE 5
(1) Synthesis of 2-(N-tert-Butylsulfamoyl)~ 4-(2-methoxy-
- ethoxy)-5-sulfophenylazo]-5-methanesulfonamido-1-naphthol
To a solution containing 1.7 g of sodium hydroxide
and 8 m~ of water, 9.9 g of sodium 5-amino-2(2-methoxyethoxy)-
benzenesulfonate and then 10 m~ of an aqueous solutioncontaining 2.8 g of sodium nitrite were added. The solution was
added dropwise to a solution containing 18 m.Q of conc. hydro-
chloric acid and 70 m~ of water at a temperature below 5C. The
mixture was stirred for 30 minu-tes at below 5C to complete
the reaction.
To a solution containing 8.0 g of sodium hydroxide,
40 m~ of water and 150 mQ of methyl alcohol, 14.9 g of 2-tert-
butylsulfamoyl-5-methanesulfonamido-1-naphthol was added. To
the solution thus prepared, the above described diazo solution
was added dropwise at a temperature below 10C. ~ter completion
-55-
~3~ 5
g of the addition, the mix-ture was s~irred for 30 minutes at
below 10C and 20 mi,of concentrate hydrochloric aci~ was
added thereto. The crys-tals thus precipi-tated were collected
by filtration, washed with 200 m~ of ace-tone and air-dried.
Yield: 19 g; Meltin~ Poin~: 215-220C
In the manner analogous to Step (1) in Synthesis
Example 5, the compounds tabulated below were also synthesized.
OH 3
~R
~ ~ ~ 2 ~ R4
~ (XVIIa)
CH3S02-NH N=N-~-OCH2CH20CH3
S2H
Compound No. R3 R4 m.p.
.. .. _ - - - ~ C )
XVII-l -CH3 H >250
XVII-2 -C2H5 H ~250
-: XVII--3 -CH (CH3) 2 H >250
XVII-4 -C2H5 C2H5 195-203
XVII-5 ~3H7 (n) C3H7 (n) 163-168
20 XVII-6 (C 2)4 >250
XVII-7 6 5 H >250
XVII - 8 -CH3 -CH3 ~250
XVII-9 4 9~ ) -C4H9(n) 156-160
XVII--lQ --CH2CH20CH3 H 248-250
* R3 and R are combined to form -(CH2)4-
(2) Synthesis of 2-(N-tert-Butylsulfamoyl)-4-[4-(2 methoxy-
ethoxy)-5-chlorosulfonylphenylazo]-5-methanesulfonamido-1-
naphthol
To a solution containing 19 g of 2-(N-tert-butyl-
30 sulfamoyl)-4-[4-(2-methoxyethoxy)-5-sulfophenylazo]-5-methane-
-56-
. :,- ;.
:~IL3~L8S
1 sulfonamido-l~naphthol preparecl as described in Step (1) above,
loo m~of acetone and 20 m~'~ of phosphorous oxychloride, 20 m~ of
N,N-dimethylacetamide was added dropwise at a temperature below
50~C. After completion of the addition, the mix-ture wa5
stirred for 1 hour and was poured gradually into 500 mQ of ice
water. The crystals thus precipitated were colleated by
filtration, washed with 50 m.~ of acetonitrile and air-dried.
Yield: 14 g; Melting Point: 148--153C
In the manner analogous to Step (2) in Synthesis
Example 5, the compounds tabulated below were also synthesized.
OH ~ R3
~ / ~ SO2N~ R4 (Xa)
CH3S02NH N=N~>- OCH2CH20CH3
S02C -~
Compound No. R3 R4 m p.
... _ ( C )
X-l -CH3 H 115-120
X-2 2 5 H 190-194
X-3 -CH(CH3)2 H 175-177
X-4 C2 5 C2 5 167-168
X-5 3 7( ) 3 7( ) 153-155
X-6 (C 2)4 184-187
X-7 C6H5 H 115-120
X-8 -CH3 -CH3 200-205
X-9 -C4H9(n) -C4H9(n) 156-160
*R3 and R4 are combined to form -(CH2)4-
(3) Synthesis of Compound 1
To 40 m~ of N,N-dimethylacetamide, 20 g of 2-amino-4-
~L~3:~85
1 hexadecyloxy-5-methylphenol hydrochloride and 13 g oE 2-(N-
tert-butylsulfamoy~ -[4-(2-methoxyethoxy~-5-chlorosul-Eoxyl-
phenylazo]-5-methanesulEonamido-l-naph-thol prepared as described
in Step (2) above were adcled. 10 mi9 of pyridine was added
dropwise to the mixture with stirrincJ and the mix-ture was
stirred at room temperature for 2 hours. The reaction mixture
was poured into a mixture o~ 10 m~ of hydrochloric acid and
200 m~ of ice water. The crystals thus precipitated were
collected by filtration, washed with water, air-dried and
recrystallized from 50 m~ of methyl alcohol. Yield: 5.0 g;
Melting Point: 140-142C
SYNTHESIS EXAMPLE 6
(1) Synthesis of 2-Pyrrolidinosulfonyl-4-54-(2-methox~ethoxy)-
5-sulf ~ -5-methanesulfonamido-1-naphthol
To a solu-tion containing 0.9 g of sodium hydroxide
and 40 m~ of water, 4.9 g of sodium 5-amino-2-(2-methoxyethoxy)-
benzenesulfonate and then 5 m~ of aqueous solution containing
1.4 g of sodium nitrite were added. The solution was added
dropwise to a solution containing 9 mQ of concentrated hydro-
chloric acid and 36 m~ of ice water at a tempera-ture below 5C.
The mixture was stirred for 30 minutes at below 5C to complete
the reaction.
To a solution con-taining 4.0 g of sodium hydroxide,
20 mQ of water and 40 m~ of methyl alcohol, 7.4 y of 2-
pyrrolidinylsulfamoyl-5-methanesulfonamido-1-naphthol was added.
To the solution thus prepared, the above-described diazo
solution was added dropwise at a temperature below 10C. After
completion of the addition, the mixture was stirred for 30
minutes and 10 m ~of concentrated hydro~hloric acid was
added thereto. The crystals thus precipitated were collected
-58-
by filtra-tion, was~l~d with 100 m~q of ace~one and air-dried.
Yield: 3.7 g; Melting Point: above 250C
~2) Synthesis o~ 2-Pyrrolidinosulfonyl-~-[~-(2--methoxyethoXy)-
5-chlorosulEonylphenylazo]-5-methanesulfonamido-L naph-thol
To a solution conta:ininy 8.7 g of 2-pyrrolidino-
sulfonyl-4-[4-(2-methoxyethoxy)-s-sulfophenylazo]-5-methane-
sulfonamido-l-naphthol prepared as described in Step (1) above,
40 mQ of acetone and 9 m~of phosphorous oxychloride, 9 mL9Jof
N,N-dime-thylacetamide was added dropwise at a tempera-ture below
50C. After completion of the addition, the mixture was
stirred for 1 hour at room temperature and was poured into 200
m;Q of ice water. The crystals thus precipitated were collec-ted
by filtration and washed with 20 m~Q of acetonitrile. Yield:
5.0 g; Melting Point: 184-187C
(3) Synthesis of Compound 3
To 20 m~ of N,N-dimethylacetamide, 3.1 g of 2-amino-
4-hexadecyloxy-5-methylphenol hydrochloride and 5.0 g of 2-
pyrrolidinosulfonyl-4-[4-(2-methoxyethoxyj-5-chlorosulfonyl-
phenylazo]-5-methanesulfonamido-1-naphthol prepared as described
in Step (2) above were added. 3.6 m~ of pyridine was added
dropwise to the mixture with stirrin~ and the mixture was
stirred at room temperature for 2 hours. After completion of
the reaction, 30 mQ of methanol and 10 m~ of water were added
to the reaction solution~ The crystals thus precipitated were
collected by filtration, washed with 50 m~- of methanol, air-
dried and recrystallized from 50 m~ of acetonitrile. Yield:
4.0 g; Meltin~ Point: 105-108C
SYNTHESIS EXAMPLE 7
. ~ .. . . _ ....
S~nthesis of Compound 18
.. __ A . _ . _ ._ _
(a) Synthesis of 2-(2-Methoxyethoxy)-5-nitrobenzenesulfonyl
Chloride
-59-
. , .
~31~3S
1 59 g of sodium 2-(2-methoxyethoxy)-5-nitrobenzene-
sulfonate prepared as described in Syn-thesis Exarnple 1 was added
to a mixture of 200 m~- of acetone and 75 m'~of phosphorous
oxychloride. 75 m ~of N,N-d:ime~hylacetamide was added dropwise
to the mixture with stirring while the reaction mixture was
maintained at 30 to 40C. After completion of the addition,
the mixture was allowed to stand with stirring until it cooled
to room temperature. The reaction mixture was then poured into
600 m.e of ice water, stirred for 30 minutes and the crystals
thus preciptated were collected by filtration. The crystals were
washed wlth 100 m~of water and air-dried. Yield: 56 g; Melting
Point 74-74.5C
~b) Synthesis of 2-[2'-(2-Methoxyethoxy)-5'-nitr~benzene
sulfonamido]-4-hexadecyloxy-5-methylphenol
20 g of 2-amino-4-hexadecyloxy-5-methylphenol hydro-
chloride and 18 g of 4-(2-methoxyethoxy)nitrobenzene-3-sulfonyl
chloride prepared as described in Step (a) above were added to a
mixture of 100 m~ of tetrahydrofuran and 10 m~ of pyridine and
the mixture was stirred at room temperature for 3 hours. The
reaction mixture was added to a mixture of 300 mQ of ice water
and 50 m~ of concentrated hydrochloric acid with stirring. The
crystals thus-precipitated were recovered with filtration,
washed with water, air-dried and recrystallized from 100 m~of
acetonitrile. Yield: 35 g; Melting Point: 85.5-86C
(c) Synthesis of 2-[2'-(2-Methoxyethoxy)-5'-aminobenzene-
sulfonamido]-4-hexadecyloxy-5-methylphenol
32 g of 2-[2'-(2-methoxyethoxy) -5'-nitrobenzene-
sulfonamido]-4-hexadecyloxy-5-methylphenol prepared as described
in Step (b) above, 24 g of iron powder, 12 g of Fe3O4, 0.6 g of
ammonium chloride and 25 mQ of water were added to 300 mQ of
-60-
: ~ , , ,.,; .
:. : .
~3~9~85
1 isopropyl alcohol and the mixtu~e was reflu~ed on a .steam bath
with stirrin~ for 1 hou~. AEter comple~ion of the reaction, the
mixtur~ was filtered ~hile hot and the ~iltra-te was cooled wi-th
ice. The crystals thus precipitated were recovered by fil-tration,
washed with 50 mi of isopropyl alcohol and air-dried. Yield:
23 g; Meltiny Point: 142 to 144C.
(d) Synthesis of Compound 18
... . . _ ... .
To 10 m~ of N,N-dimethylacetamide, 3.8 g of 2~tert-
butylsulfamoyl-4-[4-(2-methoxyethoxy)-5-chlorosulfonylphenylazo]- -
lQ 5-methanesulfonamido-1-naphthol prepared as described in Step (2)
of Synthesis Example 5 and 3.5 g of 2~[2-(2-methoxyethoxy)-5-
aminobenzenesulfonamido]-4-hexadecyloxy-5-methylphenol prepared
as described in Step (c) above was added. 1.8 m~ of pyridine
was added dropwise -to the mixture and the mixture was stirred
at room temperature for 2 hours. After completion of the
reaction, 15 m~ of methanol and 5 m~-of water were added to the
reaction solution. The crystals thus precipitated were collected
by filtration and recrystallized from 50 m.~ of methanol. Yield:
4.0 g; Melting Point: 117-123C
SYNTHESIS EX~MPLE 8
Synthesis of Compound 20
.. ..
To 15 m~ of N,N-dimethylacetamide, 6.5 g of 2-
pyrrolidinosulfonyl-4~[4-(2-methoxyethoxy)-5-chlorosulfonyl-
phenylazo ]-5-methanesulfonamido-1-naphthol prepared as described
in Step (2) of Synthesis Example 6 and 5.9 g of 2-[2-(2-methoxy-
ethoxy)-5-aminobenzenesulfonamido]-4-hexadecyloxy-5-methylphenol
prepared as described in Step (c) of Synthesis Example 7 were
added. 1.6 m~ of pyridine was added dropwise to the mixture
and the mixture was stirred at room temperature for 2 hours.
Ater completion of the reaction, 20 m~ of methanol and 10 miQ of
-61-
s
1 water were added to the reac-tion mix-ture. The crystals thus
precipitated were collecte~ by filtration, washed with 50 m~ oE
methanol~ air-dried and recrys-tal]ized Erom 200 m.~)oE ace-tonitrile.
Yield: 9.5 g; Meltin~ Point: 1~3-1~6C
In the reproduction of natural color by subtractive
color photography, a light-sensitive element comprisiny at least
two combinations of each o~ a silver halide emulsion having a
selective spectral sensitivity in a cer~ain wavelength region and
a compound capable of pxoviding a dye having a selective
spectral absorption at the same wavelength region as the emulsion
is used. In particular, a light-sensitive element comprising a
combination of a blue-sensitive silver halide emulsion and a
compound capable of providing a yellow dye, a cvmbination of a
green-sensitive silver halide emulsion and a compound capable of
providing a magenta dye, and a combination of a red-sensitive
silver halide emulsion and a compound capable of providing a
cyan dye is useful. As a matter of course, diffusible dye-
releasing redox compounds of the present invention can be used
as the above-described compounds capable of providing the dye.
These combinations of units of the silver halide emulsions and
the dye providing compounds may be coated on a support as layers
in a face-to-face relationship or may be coated on a support as
a layer containing a mixture of particles of the si~ver halides
and the dye providing compounds in a binder.
In a preferred multilayer structure, a blue-sensitive
silver halide emulsion layer, a green-sensitive silver halide
emulsion layer and a red-sensitive silver halide emulsion layer
are positioned in this order from the side of incident light
of exposure and, in particular, it is desirable for a yellow
filter layer to be postiioned between the blue-sensitive silver
-5~-
,
,
: .
~3~4~5
1 halide emulsion layer and the green-sensiti-ve silver halide
emulsion layer ~hen a highly sensitive silver halide emulsion
containin~ silver iodide is used. The yellow filter layer
usually contains a dispersion of yellow colloidal silver, a dis-
persion of an oil-soluble yellow dye, an acid dye mordanted to
a basic polymer, or a basic dye mordanted to an acid polymer.
It is advantageous for the silver halide emulsion layers
to be separated from each other by an interlayer. The interlayer
acts to prevent the occurrence of undesirable interactions
between the differently color-sensitized silver halide
emulsion layers. The interlayer employed in such a case is
usually composed of a hydrophilic polymer such as gelatin,
polyacrylamide, a partially hydrolyzed product o-E polyvinyl
acetate, etc., a polymer containing fine pores formed from a
late~ of a hydrophilic polymer and a hydrophobic polymer, e.g.,
as described in U.S. Patent 3,625,685, or a polymer whose
hydrophilic property is gradually increased by the processing
composition, such as calcium alginate, as described in U.S.
Patent 3,384,~83, individually or as a combination thereof.
Generally speaking, except where noted otherwise, the
silver halide emulsion layers employed in this invention com-
prise photosensitive silver halide dispersed in gelatin and are
about 0.5 to about 20 ~ thick, preferably 0.6 to 6 ~ thick; the
dye image providing materials are dispersed in an aqueo~ls
alkaline solution-permeable polymeric binder, such as gelatin,
as a separate layer about 0.5 to about 20 ~ thick, preferably
1 to 7 ,u thick; and the alkaline solution-permeable polymeric
interlayers, e.g., gelatin, are about 0.5 to about 20 p thick,
preferably 1 to 5 ,u thic]c. Of course, these thicknesses
are approximate only and can be modified according to the
pxodu~t desired.
- 63 -
~3~8~;
1 The silver halide emulsions which can be used in the
pxesent invention are a dispersion of silver chlori~e, silver
~romide, silver chlorobromide, silver iodobromide, silver
chloroiodobromide or a mixture thereof in a hydrophilic colloid.
The halide composition of the silver halide is selec-ted depending
on the purpose oE using the photographic materials and the
processing conditions for the photographic materials, but a
silver iodobromide emulsion or a silver chloroiodobromide emulsion
having a halide composition of 1 to 10 mol% iodide, less than
30 mol~ chloride, and the rest bromide is particularly pre-
ferred. The grain size oE the silver halide used may be aconventional grain size or a fine grain size but silver halides
having a mean grain size of from about 0.1 micron to about 2
microns are preferred. Furthermore, depending on the speciEic
purpose of using the photographic materials, it is sometimes
desirable to use a silver halide having a uniform grain size.
~ The silver halide grains used in the present invention may have
the form of a cubic system, an octahedral system, or mixed
crystal system thereof. These silver halide emulsions may be
prepared using conventional methods as described in, for example,
P. Grafkides, Chimie Photographique, Chapters 18-23, 2nd Edition,
Paul Montel, Paris (1957).
The silver halide emulsions used in the present
invention are preferably chemically sensitized,e.g., by heating
using the natural sensitizers contained in gelatin, a sulfur
sensitizer such as sodium thiosulfate or N,N,N'-trimethyl-
thiourea, a gold sensitizer such as a thiocyanate complex salt
or thiosulfate complex salt of gold, or a reducing sensitizer
such as stannous chloride or hexamethylenetetramine.
Also, silver halide emulsions which form a latent image
- 64 -
:1~3~5
1 on the surface of the silver halide grains, s:iLve~ halide
emulsions which form a laten-t image inside ~he silver halide
grains as described in U.S. Patents 2,592,550, 3,206,313, etc.,
and direct positive silver halide emulsions can be used in the
present invention.
A suitable coating amount of the emulsion ranges from
about 0.1 g/m2 to 10 g/m2, preferably 0 3 g/m2 to ~ g/m2 (silver
per m2 of the support). A suitable amount of the dye image-
providing material of this invention can range from about 0.01
10 to about 10 mols, preferably Q.05 to 0.5 mol, per mol of the
silver halide.
The silver halide emulsions used in the present in-
vention may be stabilized with additives such as 4-hydroxy-6-
methyl-1,3,3a,7-tetrazaindene, 5-nitroimidazole, 1-phenyl-5-
mercaptotetrazole, 8-chloromercuriquinoline, benzenesulfinic
acid, pyrocatechin, 4-methyl-3-sulfoethylthiazolidin-2-thione,
4-phenyl-3-sulfoethylthiazolidin-2-thione, etc., if desired.
In addition, inorganic compounds such as cadmium salts, mercury
salts, complex salts of platinum group metals such as the
chloro complex salt of palladium, and the like are also useful
for stabiliziny the light-sensitive material of the present
invention. Furthermore, the silver halide emulsions used in
the present invention may contain sensitizing compounds such
as a polyethylene oxide compound.
The silver halide emulsions used in the present in-
vention can possess, if desired, a color sensitivity expanded
with a spectral sensitizing dye or dyes. Examples of useful
spectral sensitizers are cyanine, merocyanine, holopolar
cyanine, styryl, hemicyanine, oxanole, hemioxanole, etc., dyes.
Specific examples of suitable spectral sensitizers which can be
- 65 -
4~5
1 used in this invention are described in, for example, P.
Grafkides, sup.ra, Chapters 35-41, and F.M. Hamer, The Cyanine
Dyes and Related Compounds, Interscience. A par-ticularly useful
spectral sensitizer is a cyanine of which the nitrOCJen atom of
the basic heterocyclic nucleus has been substituted with an
aliphatic group (e.g., an alkyl group) having a hydroxy group,
a carboxy group, or a sulfo group as described in, for example,
U.S. Patents 2,503,776, 3,459,553 and 3,177,210.
The dye image providing material used in this invention
can be dispersed in a hydrophilic colloid using various
techniques, depending on the type of dye image providing material.
For example, when the dye image providing material has a
dissociable group such as a sulfo group or a carboxy group, the
dye image providing material can be added to an aqueous solution
of a hydrophilic colloid as a solution in water or as an aqueous
alkaline solution thereof. On the other hand, when the dye
. image providing material is sparingly soluble in aqueous
medium but is readily soluble in organic solvents, the dye
image providing material is first dissolved in an organic solvent
and then the solution is finely dispersed in an aqueous
solution of a hydrophilic colloid with stirring. 5uch a dis-
persing method is described in detail in, for example, U.S.
Patents 2,322,027, 2,801,171, 2,949,360 and 3,396,027.
The concentration of the dye image provi~ing materials
that are employed in the present invention may be varied over
a wide range depending upon the particular compound employed
and the results which are desired. E`or example, the dye
image providing compounds of the present invention may be
coated in layers by using coating solutions containing about
0 5 to about 15% by weight, preferably containing 0.5 to ~% by
- 66 -
. .: , .
~,
8~
1 weight, of the dye image providing compound distributed in a
hydrophilic film forming natural material or synthetic polymer,
such as gelatin, polyvinyl alcohol, etc.
To stabilize the dispersion of the dye image providing
material and also to promo-te dye imaye formatlon, it is
advantageous to incorporate the dye image providing material
into an aqueous hydrophilic colloid solution as a solution in
a solvent which is substantially insoluble in water and has a
boiling point of higher than about 200C at normal pressure.
Examples of suitable hi~h boiling solvents which can be used
for this purpose are aliphatic esters such as the triglycerides
of higher fatty acids, dioctyl adipate, etc.; phthalic acid
esters such as di-n-butyl phthalate, etc.; phosphoric acid
esters such as tri-o-cresyl phosphate, tri-n-hexyl phosphate,
etc.; amides such as N,N-diethyllaurylamide, etc.; and hydroxy
compounds such as 2,4-di-n-amylphenol. Furthermore, to
stabilize the dye image providing material and to promote dye
image formation, it is also advantageous to incorporate an
oleophilic polymer into the photosensitive layer together with the
dye image providing material. Examples of suitable oleophilic
polymers which can be used ~or this purpose are shellac, a
phenol-formaldehyde condensate, poly n-butyl acrylate, a
copolymer of n-butyl acrylate and acrylic acid, an interpolymer
of n-butyl acrylate, styrene, and methacrylamide, etc.
Such an oleophilic polymer may be dissolved in an
organic solvent together with the dye image providing material
and then may be dispersed in a photographic hydrophilic colloid
such as gelatin as a solution thereo~ or ma~ be added to a
dispersion in a hydrophilic colloid of the dye-releasing redox
compound as the hydrosol of a polymer prepared by emulsion poly-
merization, etc.
- 67 -
1 The ra-tio of dye image-providing material to polymer
can be about 0.1 to about 10, preferably about 0.25 to about 5.
The dispersion of the d~e image providing material
is generally carried out using a large shearing s-tress. For
instance, a high speed mixer, a colloid mill, a high pressure
milk homogeni2er, a high pressure homogenizer as described in
British Patent 1,304,264, an ultrasonic emulsifying device,
etc., are suitably used.
The dispersion of the dye image providing material can
be greatly promoted by using a surface active agent as an
emulsification aid. Examples o~ suitable surface active agents
useful for dispersion of the dye image providing material used
in this invention are sodium triisopropylnaphthalenesulfonate,
sodium dinonylnaphthalenesulfonate, sodium p-dodecylbenzene-
sulfonate, sodium dioctylsulfosuccinate, sodium cetylsulfate,
and the anionic surface active agents as described in Japanese
Patent Publication No. 4,293/1964 and British Patent 1,138,514.
The use of these anionic surface active agents and the higher
fatty acid ester of anhydrohexitol exhibits particularly
excellent emulsifying capability as disclosed in U.S. Patent
3,676,141. A suitable amount o the surface active agent ranges
from about 1% to about 20% by weight per gram of the dye
image providing material Furthermore, the dispersing methods
disclosed in Japanese Patent Publication No. 13837/1968 and
U.S. Patents 2,992,104, 3,044,873, 3,061,428 and 3,832,173 can
be effectively employed for dispersing the dye image providing
material used in this invention.
The light-sensitive element of the present invention
is prepared by coating directly or indirectly at least one light-
sensitive silver halide photographic emulsion layer with the dye
- 6~ -
3S
image providing matexial accor~ing to the present invention
associated therewith onto a substantially planar material
which does not undergo large dimensional changes. Examples
of suitable supports which can be used are cellulose acetate
films, polystyrene films, polye~hylene terephthalate films,
polycarbonate films, etc., as are used as suppor-ts for con-
ventional photographic materials. Other examples of suitable
supports are papers and papers coated with a water-impermeable
polymer such as polyethylene.
The methods described in U.S. Patents 3,928,312, 3,931,1~4
and 3,954,476, and Belgian Patent 788,268 can be employed
as methods of forming diffusion transfer color photographic
images by using dye image providing material. 'r`hese image
forming methods can be effectively used with the dye image pro-
viding material according to the present invention.
One embodiment of a series of steps for obtaining color
diffusion transfer images using a dye-releasing redox compound
according to the present invention is described below.
(A) ~ light-sensitive element comprising a support having
thereon at least one light-sensitive silver halide emulsion layer
with the dye-releasing redox compound according to the present
invention associated therewith is imagewise exposed,
(B) An alkaline processing composition is spread on the above-
described light-sensitive silver halide emulsion layer whereby
development of all light-sensitive silver halide emulsion
layers in the presence of a developing agent for silver halide
is conducted.
(C) As a result, an oxidation product of the developing agent
produced in proportion to the amount of exposure cross-oxidizes
the dye-releasing redox compound.
- 69 -
8~
1 (D ) The ~bove-d~sc~ibed oxld~tlon product of the dye-releasincJ
redox compound splits to xelease a diffusible dye.
(E) The released diffusible dye imagewise diffuses to form a
transferred image on an image-receiving layer (directly or
indirectly) adjacen-t the ligh-t-sensitive silver halide
emulsion layer.
In the above-described process, any silver halide develop-
ing agents which can cross-oxidize the dye-releasing redox
compound can be used. These developing agents may be in-
corporated into the alkaline processing composition or may be
incorporated into appropriate photographic layers of the light-
sensitive element. Specific examples of suitable developing
agents which can be used in this invention are, for example,
hydroquinones; aminophenols such as N-methyl-aminophenol;
pyrazolidones such as l-phenyl-3-pyrazolidone, 1-phenyl-4,4-
dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-oxymethyl-3-
pyrazolidone; phenylenediamines such as N,N-diethyl-p-phenylene-
diamine, 3-methyl-N,N-dietnyl-p-phenylenediamine, 3-methoxy-N-
ethoxy-p-phenylenediamine; etc.
Of the above-indicated developing agents, black-and-
white developing agents having the capability, in general, of
reducing the occurrence of stains in image-receiving la~ers
are particularly preferred in comparison with color developing
agents such as phenylenediamines.
When tne dye-releasing redox compound according to
this invention is used, the transferred image formed in the
image-receiving layer is a negative image and the image remaining
in the photosensitive layer is a positive image where a con-
ventional surface latent image forming type emulsion is used
without using a reversal mechanism. On the other hand, where
- 70 ~
1 a direct positive silver halide emulsion (including an
emulsion whic~n can provide a ~irect reversal positive iMage by
fogging durincJ development after exposure, Eor example, an
internal latent image forming type si:Lver halide emulsion or
a solarization type silver halide emulsion) is employed as -the
silver halide emulsion in the above-described case, the
transferred image formed in the image-receiving layer is a
positive image.
Solarization type silver halide emulsions as described
in C.E K. Mees, The Theory of the Photographic Process, pages
... _ _ . .. .
261-297, Macmillan Co., New York (1942) can be used in this
invention. These solarization type silver halide emulsions
may be prepared using methods described in, for example, British
Patents 443,245 and 462,730 and U.S. Patents 2,005,837,
2,541,472, 3,367,778, 3,501,305, 3,501,306 and 3,501,307.
Also, internal latent image forming type silver halide
emulsions as described in, for example, U.S. Patent 2,592,250,
can be advantageously used in this invention. T~pical
examples of fogging agents which can be used for preparing this
~ type of silver halide emulsion are the hydrazines described in
U.S. Patents 2,588,982 and 2,563,785, the hydrazine and hydrazone
described in U.S. Patent 3,227,552, and the quaternary salt
compounds described in British Patent 1,283,835, Japanese
Patent Publication No. 38164/1974, and U.S. Patents 3,734,738~
3,719,494 and 3,615,615. The amount of fogging agent employed
can be widely varied depending upon the results desired. In
general, the concentration of fogging agent is from about 0.1
to about 15 g per mol of silver, preferably from about 0.4 to
about 10 g per mol of silver in the photosensitive layer in the
photosensitive element.
: .
1 Furthermore, the di~fusion inhibitor releasing (DIR)
reversal silver halide emulsion system as described in U.S.
Patents 3,227,551, 3,227,554 and 3,36~,022 or ~he reversal silver
halide system using dissolution physical development as
described in British Patent 904,364 can be employed in the case
of using the dye-releasing redox compound of this invention.
The dye image providing material according to the
pxesent invention can be used ~ogether with a dye image providing
material having an absorption in a longer wavelength region,
if desired. The molar ratio of the compouna of the present
invention in a mixture ranges from about 1 to about 70%, pre-
ferably 1 to 50%. Compounds which provide a transferred image
having an absorption maximum at 545 to 600 nm are desirable dye
image providing material to be used with the compound of the
present invention. A dye image providing material having an
absorption in a longer wavelength region can be incorporated
into a layer containing the compound according to the present
invention or into another preferably adjacent layer. A dye
image providing material having an absorption in a longer
wavelength region is preferably changed temporarily to a compound
having an absorption in a short wavelength in a dispersion in
view of color reproduction.
It is necessary for the image-receiving element used in
this invention in combination with the above-described light-
sensitive element to have an image-receiving mordan-ting layer
comprising a mordant, such as the poly-4-vinylpyridine latex
(in, preferably, polyvinyl alcohol) described in U.S. Patent
3,148,061, the polyvinyl pyrrolidone described in U.S. Patent
3,003,872, and the polymers containing quaternary ~mmonium salts
as described in U.S. Patent 3,239,337, individually or as a
- 72 -
~' `~' -
~L~L3~485
1 combination the~eor. Also, the basic polymers as described in
U.S. Patents 2,882,156, 3,625,694 and 3,709,690 can be eEEectively
used as the mordant ~or the image-receiving layer. Other
examples of mordants which can be effectively used in this
invention are described in U.S. Patents 2,484,430, 3,271,147,
3,184,309, etc.
Preferably the light-sensitive sheet of this invention
is capable of neutralizing the alkali carried in from the
alkaline processing composition. It is advantageous for this
purpose for the li~ht-sensitive sheet to include in a cover
sheet or in an image-receiving elemen~ thereof a neutralizing
layer containing an acid material in an amount sufficient to
neutralize the alkali in the liquid processing composition,
that is, containing an acid material at an area concentration
higher than the equlvalent of the alkali in the spread liquid
processing composition. When a cover sheet having a neutrali~ing
layer is used, the cover sheet can be superimposed on an image-
receiving layer after such has been peeled from a light-sensitive
element. Typical examples of preferred acid materials which
~0 can be usecl for this purpose are those described in U.S. Patents
2,983,606, 2,584,030 and 3,362,819. The neutralizing layer may
further contain a polymer such as cellulose nitrate, polyvinyl
acetate, etc., and also the plastici~ers as described in U.S.
Patent 3,557,237 in additlon to the acid material. The acid
material may be incorporated in the light-sensitive sheet in
a microencapsulated form as described in German Patent
Application (OLS) No. 2,038,254.
It is desirable for the neutralizing layer or the
acid material-containing layer which can be used in this
invention to be separated from the spread layer of the liquid
1 processiny composition by a neutralization rate contxol]in~
layer (or timing layer). Gelatin, polyvinyl alcohol, or the
compounds describecl in U.S. Patents 3,455,686, ~,009,030 and
3,785,815, Japanese Patent Application No. 779~6/1957 and
90616/1975, Japanese Patent Application (OPI) Nos. 92022/1973,
64435/1974, 22935/197~ and 77333/1976, Japanese Pa-tent Publi~
cation Nos. 15756/1969, 12676~'1971 and 41214/1973, German Patent
Application (OLS) Nos. 1,622,936 and 2,162,227, Research
Disclosure, No. 151, 15162 (1967)~ etc., can be effectively
.. . ..
1~ used as the timing layer. The timing layer acts to retard the
reduction in the pH of the liquid processing composition by
the neutralizing layer until the desired development and trans-
fer of dyes can be sufficiently accomplished.
In a preferred embodiment of this invention, the image
receiving element has a multilayer structure comprising a support,
a neutralizing layer, a timing layer, and a mordanting layer
(or image-receiving layer) in this order. Image-receiving
elements are described in detail in, for example, Japanese
Patent Application (OPI) No. 13285/1972, U.S. Patent 3,295,970
and British Patent 1,187,502.
The processing composition of the processing element
used in this invention is a liquid composition containing the
processing components necessary for developing silver halide
emulsions and forming diffusion transfer dye images. The
solvent of the processing composition is mainly water and
contains, as the case may be, a hydrophilic solvent such as
methanol, methyl Cellosolve, etc. The liquid processing com-
position contains alkali in an amount sufficient to maintain
the necessary pH on developing the silver halide emulsion layers
and for neutralizing acids te-g-, hydrohalic acids such as
- 7~ -
; . .
s
1 hydrobromic acid, e-tc., ancl carboxylic acids such as acetic
acid, etc ) formed during clevelopment and dye image Eorma-tion.
Examples of suitable alkalis are hydroxides or salts of ammonia,
al~ali metals or alkaline earth metals or amines, such as
lithium hydroxide, sodium hydroxide, potassium hy~roxide, an
aqueous dispersion of calcium hydroxide, tetramethylammonium
hydroxide, sodium carbonate, trisodium phosphate, diethylamine,
etc. It is desirable for thie liquid processincJ composition to
eontain an alkaline material in a eoneentration sueh that the
~0 pH thereof ean be maintained at above about 12, in partieular,
above 1~ at room temperature. Further preferably, the liquid
proeessing eomposition eontains a hydrophilic polymer such as
high moleeular weight polyvinyl aleohol, hydroxyethyl eellulose,
sodium earboxymethyl eellulose, etc. ~hese polymers contribute
toward increasing the viseosity of the liquid processing
eomposition above about 1 poise, preferably to 500 or 600 to
1,000 poises, at room temperature, whieh faeilitates the
uniform spreading of the processing eomposition at development
as well as the formation of a non-fluid film when the aqueous
medium has diffused into the photosensitive element and the
image-reeeiving element during proeessing thereby coneentrating
the proeessing eomposition, whieh results in assisting uni-
fieation of all of the elements after proeessing. The polymer
film also eontributes toward preven-ting eoloring eomponents
from transferring into the image-reeeiving layer to stain the
dye images formed after the formation of the diffusion transfer
dye image is substantially eompleted.
As the ease may be, it is advantageous for the liquid
proeessing eomposition to further contain a light absorbing
material sueh as Tio2, earbon blaek, a pH indieating dye, etc.,
- 75 -
~3~ 5
1 or the desensiti~er as described in U.S. Patent 3,579,333 for
preventing the sil~-er halide emulsion laye~s from belng
fogged by ambient light durin~ processing outside the camera.
~urthermore, the liquid processing composition used in this
invention may contain a development inhibitor such as benzo-
triazole.
It is preferred for the above-described processing
composition to be retained in a rupturable container as described
in U.S. Patents 2,543,181, 2,643,886, 2,653,732, 2,723rO51,
lO 3,056,491, 3,056,~92, 3,152,515, etc.
As the developer, any developer that can cause the
oxidation-reduction reaction between exposed silver halide
and the DRR compound may be used. For example, ordinary color
developers or black-and-white developers are included. Of
these, blàck-and-white developers are particularly preferable.
In the case of using a diffusible dye-releasing compound with
other dye image-providing materials, all that is required is
to use a conventional color developer upon processiny in a
manner with which the artisan is well acquainted. Where a dye
developing agent is used as the dye image-providing material,
it is not necessary to use other developing agents upon pro-
cessing. However, it is preferable to use an auxiliary Aevelop-
ing a~ent (e.g., an ordinary black-and-white developing agent ).
The light-sensitive film unit of the present invention
which has a construction such that after imagewise exposure,
the pxocessing of the film unit is performed by passing the
film unit through a pair of juxtaposed pressure-applying members
comprises:
(1) a support,
(2) a light-sensitive element as described above,
~ 76 -
t~
1 (3) an image-receiving elelllent as described above,
(~) a processing element as described above, and
(5) a developing agent (which can be incorporated into the
processin~ element or the light-sensitive element).
~ ccording to one emb~iment of the film unit
described above, the light-sensitive element and the image-
receiving element are superimposed in a face-to-face relation-
ship, and the unit is processed, a'ter exposure, by spreading
an alkaline processing composition between bo-th elements. In
this case, the image-receiving element may be stripped off after
the transfer of the dye images has been completed or the dye
images formed in the image-receiving layer may be observed
without stripping the image-receiving element as described in
U.S. Patent 3,415,645.
In another embodiment of the film unit as described above,
the image-receiving element and the light-sensitive element are
positioned in this order in the film unit on a support. For
example, a suitable photographic film unit is prepared by coating
on a transparent support an image-receiving layer, a sub-
stantially opaque light reflecting layer (for example, a Tio2-
containing layer and a carbon black-containing layer) and a
single or a plurality of light-sensitive layers as described
above, in this order, as disclosed in Belgian Patent 757,960.
After exposing the light-sensitive element, the light-sensitive
element is super-imposed on an opaque cover sheet in a face-to-
face relationship and then a liquid alkaline processing com-
position is spread` between them.
Another embodiment of the superimposed and integral type
film unit to which the present invention is most preferably
applicable is disclosed in Bel~ian Patent 757,959. According to
- 77 -
.,
this embodiment, the film unit is prepared by coating on a
transparent support an image-receiving layer, a substantially
opaque light re~lective layer (~s described ab~ve), and a single
or a pl~rality of light-sensitive layers as described above,
in this order, and further superimposi.ng a transparent cover
sheet on the light-sensitive layer in a face-to-face relation-
~ship. A rupturable container retaining an alkaline processing
composition having incorporated therein a light-in-tercepting
agent such as, for example, carbon black, is disposed adjacent
1~ to and between the uppermost layer of the above-described light-
sensitive element and the transparent cover sheet. The film unit
is imagewise exposed in a camera through the transparent cover
sheet and then the rupturable container retaining the alkaline
processing composition is ruptured by the pressure-applying
members when the film unit is withdrawn from the camera to spread
uniformly the processing composition containing the opacifying
- agent between the light-sensitive layer and the cover sheet,
whereby the film unit is shielded from light and development
proceeds.
In these embodiments of film units, the neutralization
mechanism as described above is preferably incorporated therein.
In particular, the neutralizing layer is preferably positioned
in the cover sheet and, further, the timing layer is positioned
on the side .toward where the processing solution is to be
spread, if desired.
~oreover, other useful embodiments of the integral type
of film units wherein the dye image providing material of this
invention can be used are described in, for example, U.S.
Patents 3,415,644, 3,415,645, 3,415,646, 3,647,487, and
3,635,707 and German Patent Application (OLS) No. 2,426,980.
- 78 -
~13~8~
1 The present invention can provide advanta~eous eEfects
and some of -these, particul~rly, due to the introduc-tion of
R2-O-Rl-O- group, are described below.
Firstly, color images having less ligh-t-fading are
obtained because of the superiority in the light fastness of
the dyes released.
Secondly, color images with high quality are obtained
when the dye-releasing redox compound according to the present
invention is used together with other redox compounds of good
hue, since the hue of the dyes released is excellent and does
not vary with chan~es of pH.
Thirdly, the amount of dyes remaining at exposed areas
in light-sensitive elements is very small, since the trans-
ferability of the dye released is excellent. Therefore, it
is Qffective to ob~ain negative color images composed of the
unreacted dye image providing material which are obtained by
stripping off the light-sensitive element and subjecting
it to bleach processing (i.e., the negative can be easily used).
Fourthly, the dyes released are hardly subjected to
fading in a dark place due to a vinyl monomer such as acrylic
acid or butylacrylate which is present in a neutralizing layer.
The following examples are given to further illustrate
this invention in greater detail.
EXAMPLE 1
Dye Compound A represented by the followiny formula:
CH
QH I 3
~S02NH-C-CH3
CH3S02NH N--N ~ OCH2CH20CH3
S2NH
- 79 -
~1~3~35
which is released from Compound 1 accordin~ to the present
invention was dissolved in N,N-dimethylformamide (DMF) to pre-
pare a 10 3M solution. 0.25 mQ of the solution was dilu-ted
with 11.5 mQ oE DMF and a mixture of 1.25 m~ of a 10 lM
solution of butylacrylate and 12.5 mQ of a buEfer having a pH
of 5.05 (Britton-Robinson Buffer) was added thereto. The
solution was allowed to stand at room temperature (25-29C) and
the decrease of absorbance at a maximum absorption wavelength
in a visible region was measured. Assuming that the decrease
of dye A can be shown by a pseudo first order equation, a
reaction rate cons-tant of the pseudo first order reaction, i.e.,
k was determined.
The procedure described above and the remaining rate
of dye and the reac-tion ra-te constant (k) were determined with
respect to Dye Compound B represen-ted by the following formula:
QH
~502NH~CH3
CH3S02 H N= ~ OCH2CH20CH3
S02NH ~ OCH2CH20CH3
S2NH2
which is released from Compound 18 according to the present
invention.
For comparison, the remaining rate of dye and the re-
action rate constant (k) were determined in the same manner
described above with respect to Comparison Compounds C to E below:
Comparison Compound C
OIH IH3
~/ ~ S02NH IC CH3
CH3S02 El N= ~
2 2
80 -
- , :
:3 ~L3~8S
1 Comparison Compounc_
OH ICH3
~S02NH~C-C~13
3 2 N N ~ O-CH3
S2NH2
Comparison Compound E
. . _ .
1~
OH fH3
~ `1' 2 I H3
CEl~502NH N=N~3 502NH2
The results obtained are shown in Table 1 below.
TABLE 1
Reaction of Released Dye Compound with_Butylacrylate
Compound k
- (day
A 0.027
B 0.023
C (comparison) 0.072
D (comparison) 0.048
E (comparison) 0.098
It is apparent from the results shown in Table 1 that `~
Compounds A and B according to the present i.nvention have a
remarkably excellent fastness in comparison with Comparison
Compounds C to E.
- 81 -
.
L8~
1 ~X~MPLE 2
On a polyethylene terephthalate transparent support were
coated the layers descr:ibed below in the order listed to
prepare a light-sensitive sheet.
(1) Mordanting layer containing 3.0 g/m2 of a mordant shown
below:
- ( C~2-(~H 3 X'' ( CH2-CH~
. o f H 2
C6H13-l C6H13 CQ
C6~113
x:y = 50:50 (molar ratio)
and 3.0 g/m2 of gelatin.
(2) ~hite light reflective layer containing 20 g/m2 o titanium
oxide and 2.0 g/m2 of gelatin.
(3) Light-shielding layer containing 2.70 g/m2 of carbon
black and 2.70 g/m2 of gelatin.
(4) Layer containing 0~80 g/m2 of the magenta dye releasing
redox compound shown in Table 2, 0,40 g/m2 of N,N-diethyl-
laurylamide and 1.08 g/m2 of gelatin.
(5) Layer containing a green-sensitive internal latent image
type direct positive silver iodobromide emulsion (halogen
composition in the silver halide: 1 mol% of iodide, silver
amount: 1.8 g/m2; gelatin: 1.3 g/m2), 0.028 g/m2 of a
fogging agent represented by the following formula:
O O
C5Hll(t) ~ OCHC-NH ~ NH-NHC-CH3
5 11( )
- 82 -
8S
1 and 0.13 g/m2 of sodium doclecylhydroquinolle sulfonate.
(6) ~ayer containing 0,94 y/m2 oE gelatin.
Also, processing solution and a cover sheet shown below
were prepared.
Processing Solution:
l-Phenyl-4-methyl-4-hydro~ymethyl-3- 10 g
pyrazolidinone
Methylhydroquinone 0.18 g
5-Methylbenzotriazole 4.0 g
Sodium Sulfite (anhydrous) 1.0 g
Carboxymethyl Cellulose Na Salt - 40.0 g
Carbon Black 150 g
Potassium Hydroxide (28% aq. soln.) 200 cc
H2O 550 cc
The processing solution of the above composition was
; filled lnto a container rupturable with pressure by 0.8 g each.
Cover_Shee :
On a polyethylene terephthalate support were coated an
acid polyrner layer (neutralizing layer) containing 15 g/m2 of
polyacrylic acid (a 10 wt% aq. soln. having viscosity of about
l,000 cp) and a timing layer containing 3.8 g/m o~ acetyl
cellulose (hydrolysis of 100 g of acetyl cellulose forms 39.4 g
of acetyl groups), and 0.2 g/m2 of a styrene-maleic anhydride
copolymer (composition (molar) ratio : styrene : maleic anhydride ~
about 60 : 40; molecular weight: about 50rO00) to prepare a
cover sheet.
Processing Step:
The above described cover sheet was superimposed on the
above described light-sensitive sheet to form a film unit. E~posure
- ~3 -
1~14~
1 was per~ormed through a wedge having stepwise di~erent dens:ity
~rom the cover sheet side. Then, the processing solution
described above was spread between both sheets in a thickness of
85 microns (the spreading was per~ormed with assistance o~ a
pressure roller). The processing was carried out at 25C. After
processing, the transferred images were observed through the
transparent support o~ the light-sensitive sheet. The ma~imum
density and the minimum density o~ the magenta trans~erred images
formed were measured one hour a~ter the processing. Further,
the remaining ratio of magenta color image after allowing to
stand the film unit thus processed ~or 2 weeks at 60C and 100
relative humidity (fading in a dark place) and the remaining
xatio of magenta color image after exposed the film until thus
processed to a light of 17,000 lux for 3 days usin~ a fluorescent
lamp fading tester (light-fading) were determined. The results
thus obtained are shown in Table 2.
- TABLE 2
Magenta Dye
Releasing Fading
Redox D D .in a Light
~ Compound max Dark Fading _ Remarks
(remain- (rema1n-
ing ratio) ing ratio)
Compound 1 1.71 0.24 0.79 0.90 This invention
Compound 3 1.80 0.23 0.70 0.84 This invention
Compound 20 1.73 0.23 0.73 0.85 This invention
Compound Xl) 1.63 0.24 0.65 0.89 Comparison
Compound Y ) 1.62 0.24 0.43 0.75 Comparison
1) Compound in which the CH3OCH2CH2O- group in Compound 1
is substituted with a hydrogen atom.
2) Compound in which the CH3OCH2CH2O- group in Compound 3
is substituted with a hydrogen atom.
- 84 -
L3~
1 It is apparent from the resul-ts shown in Table 2 tha-t
magenta color images havillg a high maximum density and an
. excellent stability are obtained when the compounds according
to the present invention are used. E'urther, the magenta dye
images transferred from the compounds accordiny to the present
invention have an excellent hue and varies only to a small
extent with changes of pH (from 4 to 9).
EXA~lPLE 3
On a polyethylene terephthalate transparent support~
the layers described below in the order listed to prepare a
light-sensitive sheet.
(1) Mordant-containing layer described in Example 2.
(2) Titanium oxide-containing layer described in Example 2.
(3) Carbon black--containing layer described in Example 2.
(4) Layer containing a cyan dye releasing redox compound shown
. below (0.50 g/m2), N,N-diethyllaurylamide (0.25 g/m2)
and gelatin (1.14 g/m ).
~ OH
NH N ~ No2
2 3
502NH ~ OCH2CH20CH3
~;02N~
~ CH3
Cl 6H33
- 85 -
.: . ~ ~ .
1 (5) Layer containing a red-sensitive :internal latent image
type direct poSi tive silver iodobromide emlllsion (halogen
composition in the silver halide: 2 mol% of iodide; silver amoun-t:
1.9 g/m2; gelatin: 1.4 g/m2), a fogging agent same as desc~ibed
in Example 2 (0.028 g/m2) and sodium doclecyl~hydroquinone
sul~onate (0.13 g/m2),
(6) Layer containing gelatin (2.6 g/m2) and 2,5-di-tert-
pentadecylhydroquinone (0.8 g/m2).
(7) Layer containing compound 3 of the present invention
(0.45 g/m2), diethylenelaurylamide (0.10 g/m2), 2,5-di-tert-
butylhydroquinone (0.0074 g/m2) and gelatin (0.76 g/m2).
(8) Layer containing a green-sensitive internal latent image
type direct positive silver iodobromide emulsion (halogen
composition in the silver halide: 2 mol~ of iodide; silver
amount: 1.4 g/m2; gelatin: 1.0 g/m2), a fogging agent same as
described in Example 2 (0.024 g/m2) and sodium dodecylhydro~
quinone sulfonate (0.11 g/m ).
(9) Layer containing gelatin (2.6 g/m ) and sodium dodecyl-
hydroquinone (0.8 g/m2).
(10) Layer containing a yellow dye releasing redox compound
shown below (0.80 g/m2), diethyllaurylamide (0.16 g/m2), 2,5-
di-tert-butylhydroquinone (0.012 g/m2),
O\CH3
NC-C - IC=N-NH ~
N C=O SO2N~ ~cH2cH2ocH3
~ 2NH ~
CH3
16H33
- 86 -
i and gelatin (0.78 g/m2).
(11) I,ayer containing a blue-sensitive internal latent image
type direct positive silver iodobromide emulsion (halogen com-
position in the sil-~er halide: 2 mol~ of iodlne; silver amount:
2.2 g/m2; gelatin: 1.7 g/m2), a fogging agent same as described
in Example 2 (0.020 g/m2) and sodium dodecylhydroquinone
sulfonate (0.094 g/m2).
(12) Layer containing gelatin (0.9~ g/m2?.
A piece was cut from the light-sensitive sheet and
- exposed to light in a camera and processed using a processing
solution and a cover sheet same as described in Example 2.
Beautiful natural color transferred images having particularly
clear red color were obtained.
EXAMPLE 4
A light-sensitive sheet was prepared in the same
manner as described in Example 3 except that the compound of
the formula below:
~H
~' '
S2 1 N ~ No2
2CH3
SO NH ~ OCH CH OCH C ~ (t)
2 ~ 2 2 3 - CONH(CH2)30 ~ 5 11~ )
~2NH ~ OH
- 87 ~
1 was used in place of the cyan dye releasing redox compound,
Compound 12 was used as a ma~3enta dye releasing redox compound
and the compound of the Eormula be]ow:
OCH3
- NC- C ~ C=N- NH~
=o \= =~02NEI-~3 -OCH2CH20CH3 C~,l ( t)
~ONE~- tCH2 ) 30~C5 1:1. (
SO2NH~ ~ OH
was used in place of the yellow dye raleasincJ redox compound.
A piece of the thus obtained light-sensltive sheet was exposed
in a camera and processed in the same manner as described in
- Example 3. Beautiful natural color transferred images were
obtained.
While the invention has been described in detail and
2~ with reference to specific embodiments thereof, it will be
apparent to one skilled in the art that various changes and
modifications can be made therein without departing from the
spirit and scope thereof.
- 88 -
