CA1131485A - Photographic light-sensitive sheet containing an azo dye image providing material - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A photographic light-sensitive sheet for the color diffusion transfer process which comprises a support having thereon at least one light-sensitive silver halide emulsion layer having associated therewith a dye image providing material represented by the following general formula:

wherein Ql is selected from the group consisting of (a) a hydrogen atom, (b) a halogen atom, (c) a sulfamoyl group represented by the formula -SO2NR3R4 wherein R3 represents a hydrogen atom or an alkyl group, R4 represents a hydrogen atom or an alkyl group, an aralkyl group or an aryl group, and R3 and R4 may combine directly or through an oxygen atom to form a ring; (d) a group represented by the formula -SO2R5 wherein R5 represents an alkyl group, a benzyl group or a carboxy group, (e) a group represented by the formula -COOR6 wherein R6 represents an alkyl group, a phenyl group or a substituted phenyl group, and (f) a group represented by the formula -CONR3R4 wherein R3 and R4 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 -NHCOR4a or a group represented by the formula -NHSO2R4a wherein R4a has the same meaning as R4 defined hereinbefore, except that R4a does not represent a hydrogen atom; Rla represents an alkylene group having 2 or more carbon atoms; R2a represents an alkyl group; 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 said dye image-providing material; m is 0 or 1; q is 0 or 1; J
represents a divalent group selected from a sulfonyl 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 0 or 1; and G represents a hydroxyl group, a salt thereof, or a hydrolyzable acyloxy group represented by the formula or

Description

s 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, ~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~

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):

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 .
, .

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 ,~

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, ~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-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 ~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

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.

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 ~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.

~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) OH
~ NHSO2-C15H31 (n) OH
C~ NHS02-CH3~
OC16H33 (n) ~L~L3~5 ----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

O-CHCONH(CH2)30- ~ C5~11(t) CH
C5Hll(t) - i : . . .

~3~5 OH
C5Hll (t) ~NHS02-5 11~ OCH2CH20~-~

OH
~\~ NHS02 -5 11~ (CH2 ) 3NHCOCH--O~
105 11 (t) C 3 CH3 C5Hll t ~, CONH ( CH2 ) 3-- ~3C5Hll -t 20~rCoNH-cH-o~csHll-t .

~CNH--(CH2 ) 40~tC5Hll--t 1~3~

cNHcH2c3o ~CS~ t ~, CNH ( CH2 ) 4 0 ~1' S21~H(C~I2~,~1~15~31 OH

H31C15'~

~C01~3~

OH
CONHCl8El37 ~ .

33L48~

i~\ ,/1" ~'CNHC~12C-(CH2 ) 4-O -~ C5Hll-t NE~SO2-- 5 11 OH

~' CO(CH2)1'LCH3 OH
H31C15~3~

OH COOCl 4H2 9 (n ) ~,q, CONH~

~/ C.

OH ~ CH2CH2CN
(n) OH NHCOCH-O~ 9C5Hll (t) [~CONH ~ C2HS C5Hll (t) ~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 ~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 ~ ~ S02NH-C-CH3 CH3SO2NH N=N ~ OCH2CH20R
OH
S02NH ~

` CH3 ~)C16H33-n wherein R is CH3 , ' ' ' ~ ~

~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 ~

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.

, . : ~ .

~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 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 ~ 2 f 3 3 2 ~ OCH2CH20CH3 OH
S2NH~
~CH 3 C~--t 0CH2CONH(CH2)3-0~C5 11 Compound 12 ~ 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.

~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) ~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

wherein R2 is CH3 ~CH3 Cl ~;H33-n ~.~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 ~

OC16H33-n Compound 21 OH
~ 502NIl-R

CH3S~2 H N N ~ ~-OCH2CH20CH3 SO2NH ~ -OCH2CH20CH3 OH
SO NH

~ 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.

~13~
1 Compound 24 ~ ,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~

Compound 2 9 _ OH

~,?f ~ S02N (C2H5) 2 3 2 ~>- OCEI2CH20CEI3 OH
S02NH ,~

Cl6H33-n 10 Compound 30 ~ S2N~ R4 CH3S02 H N=N~ OH

~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

~3~5

7 Compound 34 . . .
Same compound as Compound 30 except for R3 is H and R is -CH -CH=CH ~
Compound 35 CH

~ 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

~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 ~\~ So2NH-c-cH

CH3SO2NH N=N ~ OCH2CH20CH3 02NH ~ 12 25 ( ) ~O Compound 43 ~ SO2NH-l_CH3 CH3S02NH N=N~- OCH2cH2ocH3 S02NH ~ NH-C12H25-(n) 6_~

.
, ~3~L~8~

1 Compound 44 ~J 2 ; 3 CH3S2NH N N ~ 2 2 3 O-COCH

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 -2NH-f-CH3 ~ CH3 C5~11-(t) CH3S02NH N=h4~0CH2cH20cH3 ` ~\
CONH(CH2)30 ~ C5Hll-(t) S02NH~ O-CO-COOC2H5 ~ :
/~<
W

1 Compound 47 OH ~ R3 ~ ~ 2 ~ R4 CH3S02NH N--N ~ ~-OCH2CH20cH3 S2NH 17 35 ( ) \~ .

wherein R3 and R are CH3 Compound 48 Same compound as Compound 47 except for R3 and R4 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

S02NH-~-CH3 CH3S02NH N=~OCH2CH20CH3 2 ~ ~ _NHCocl2H25-(n) -4~-,~
::

1~3~L~85 1 Compound 51 ~ 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 - . -:;

- .

~3~4~35 Q ~ O R1a ~ R2a (IX) S02NH ~ o_Rlb_o_R2b 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) 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:

~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) ~ so3 - ' ., '' .

~13~ 5 1 Compound (XVb) _ _ Compound (XVc) O-CH CH -O-C H -n ~ So2H

Compound (XVd) .

O-CH2CH -O-C4H -n 503~

~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 ~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 ~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, 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) (XVIII) Condensation ~ 1 2 Reaction ~ O2N - ~ O-R -O-R Reduction y (XIX) .

~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.

:~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 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

1131~BS

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 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 ~ .

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 (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 ~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.

~R
~ ~ ~ 2 ~ R4 ~ (XVIIa) CH3S02-NH N=N-~-OCH2CH20CH3 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-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-. :,- ;.

:~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-3 -CH(CH3)2 H 175-177 X-5 3 7( ) 3 7( ) 153-155 X-6 (C 2)4 184-187 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

(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 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

. ~ .. . . _ ....
S~nthesis of Compound 18 .. __ A . _ . _ ._ _ (a) Synthesis of 2-(2-Methoxyethoxy)-5-nitrobenzenesulfonyl Chloride . , .

~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 : ~ , , ,.,; .
:. : .

~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 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.

~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 :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 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 . .: , .
~,

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.

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~ -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.

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 ~' `~' -~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., ~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 ., 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.

~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.

Dye Compound A represented by the followiny formula:

CH

~S02NH-C-CH3 CH3S02NH N--N ~ OCH2CH20CH3 ~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 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

~/ ~ S02NH IC CH3 CH3S02 El N= ~

- , :

:3 ~L3~8S

1 Comparison Compounc_ ~S02NH~C-C~13 3 2 N N ~ O-CH3 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.

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.

.

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( ) 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.

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.

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 502NH ~ OCH2CH20CH3 ~;02N~

~ CH3 Cl 6H33 .: . ~ ~ .

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 ~

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.

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 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:

- 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.

Claims (16)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A photographic light-sensitive sheet for the color diffusion transfer process which comprises a support having there-on at least one light-sensitive silver halide emulsion layer with at least one of said silver halide emulsion layers having associated therewith a dye image providing material represented by the following general formula:

wherein Ql is selected from the group consisting of (a) a hydrogen atom, (b) a halogen atom, (c) a sulfamoyl group represented by the formula -SO2NR3R4 wherein R3 represents a hydrogen atom or an alkyl group, R4 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R3 and R4 may combine directly or through an oxygen atom to form a ring, (d) a group represented by the formula -SO2R5 wherein R5 represents an alkyl group, a benzyl group, or a carboxy group, (e) a group represented by the formula -COOR6 wherein R6 represents an alkyl group, a phenyl group or a substituted phenyl group, and (f) a group represented by the formula -CONR3R4 wherein R3 and R4 each has the same mean-ing as defined above; Q2, which is positioned at the 5- or the 8-position to the G group, represents a hydroxy group, a group represented by the formula -NHCOR4a or a group represented by the formula -NHSO2R4a wherein R4a has the same meaning as R4 defined hereinbefore, except that R4a does not represent a hydrogen atom;
1. Claim 1 continued Rla represents an alkylene group having 2 or more carbon atoms;
   R2a represents an alkyl group; 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 said dye image-providing material; m is 0 or 1; q is 0 or 1;
   J represents a divalent group selected from a sulfonyl 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 0 or 1; and G repre-sents a hydroxyl group, a salt thereof, or a hydrolyzable acyloxy group represented by the formula wherein E is selected or from the group consisting of an unsubstituted alkyl group, a sub-stituted alkyl group and an aryl group.
2. 2. The photographic light-sensitive material of Claim 1, wherein said dye image providing material is represented by the formula:
   
   wherein Rlb and R2b have the same definition as Rla and R2a and may be the same or different than Rla and R2a.
3. 3. The photographic light-sensitive sheet as claimed in Claim 1, wherein said alkylene group represented by Rla or Rlb is an alkylene group having 2 to 8 carbon atoms.
4. 4. The photographic light-sensitive sheet as claimed in Claim 1, wherein said alkyl group represented by R2a or R2b is an alkyl group having 1 to 8 carbon atoms.
5. 5. The photographic light-sensitive sheet as claimed in Claim 1, wherein said sulfamoyl group represented by Ql is a sulfa-moyl group represented by the formula -SO2NR3R4 wherein R3 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R4 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, 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.
6. 6. The photographic light-sensitive sheet as claimed in Claim 5, wherein said R3 and R4 each represents a hydrogen atom.
7. 7. The photographic light-sensitive sheet as claimed in Claim 5, wherein one of said R3 and R4 represents a hydrogen atom and the other of said R3 and R4 represents an alkyl group having 1 to 4 carbon atoms.
   
   8. The photographic light-sensitive sheet as claimed in Claim 1, wherein said Y is a sulfamoyl group represented by the following formula:
   
   wherein Ball represents a ballast group; T represents the carbon atoms necessary to complete a benzene ring, which may be
8. Claim 8 continued ...
   unsubstituted or substituted, or a naphthalene ring, which may be unsubstituted 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.
9. 9. The photographic light-sensitive sheet as claimed in Claim 8, wherein said ballast group is or contains a hydrophobic residue having 8 to 32 carbon atoms.
10. 10. The photographic light-sensitive sheet as claimed in Claim 8, wherein said ballast group is represented by the follow-ing formula:
    
    wherein R7 represents an alkylene group having 1 to 10 carbon atoms, R8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R9 represents an alkyl group having 4 to 30 carb-on atoms and R10 represents an alkyl group having 8 to 30 carbon atoms or a substituted alkyl group having 8 or more carbon atoms in which the alkyl moiety has 1 or more carbon atoms.
    11. The photographic light-sensitive sheet as claimed in claim 10, wherein said dye image providing material is represented by the formula:
11. Claim 11 continued ....
    
    wherein Rlb and R2b have the same definition as Rla and R2a and may be the same or different than Rla and R2a;
    wherein Rla and Rlb each represents a -CH2CH2- group;
    R2a and R2b, which may be the same or different, each represents an alkyl group having 1 to 4 carbon atoms; Q1 represents a hydro-gen atom or a sulfamoyl group of the formula -SO2NR3R4 wherein R3 and R4, which may be the same or different, each represents an alkyl group having 1 to 4 carbon atoms in the alkyl moiety, and 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 -NHSO2R4a group substituted at the 5-position, wherein R4a and Y have the same meanings as defined above.
12. 12. The photographic light-sensitive sheet as claimed in claim 10, wherein Rla is a -CH2CH2- group; R2a represents an alkyl group having 1 to 4 carbon atoms; Ql and Q2 each has the same meaning as defined in claim 10; Y represents an o-hydroxyphenyl-sulfamoyl group having an alkyl group at the meta position to the hydroxy group in addition to a ballast group; and m is 0.
13. 13. The photographic light-sensitive sheet as claimed in claim 1, wherein said Y is an N-substituted sulfamoyl group,
14. 14. The photographic light-sensitive sheet as claimed in Claim 1, wherein said Y is an N-substituted sulfamoyl group wherein the substituents is an o- or p- hydroxyaryl group having a ballast group bonded thereto.
15. 15. The photographic light-sensitive sheet as claimed in Claim 1, wherein said G group is a hydroxy group.
16. 16. The photographic light-sensitive sheet as claimed in Claim 1, wherein said dye image-providing material is a dye-releasing redox compound.