CA1115579A - Color diffusion transfer photographic element containing an azo yellow dye image - forming compound - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The disclosure describes a color diffusion transfer photographic element which comprises a compound represented by the formula:

(I) or (II) In the formula Al represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a nonaromatic heterocyclic active methylene containing group, a nonaromatic heterocyclic active methine-containing group, an aliphatic active methylene-containing group, an aliphatic active methine-containing group, or a group of the formula -A4-N=N-A5- (in which A4 and A5 each represent an aromatic hydrocarbon group, an aromatic heterocyclic group a nonaromatic heterocyclic active methylene-containing group, a nonaromatic heterocyclic active methine-containing group, an aliphatic active methylene-contain-ing group or an aliphatic active methine-containing group), A2 and A3 each represent an aromatic hydrocarbon group or an aromatic heterocyclic group, M1 represents a dye releasable monovalent moiety; M2 represents a dye releasable divalent moiety; Xl, X2 and X3 each represent a divalent joint group; Z

represents hydrogen or a group of the formula YCO- in which YCO
represents a hydrolyzable group; m, n and p each represent zero or a positive integer and the combined number of m, n and p is not less than 1; q, r and s? each represent zero or 1; and t, u and v each represent 0, 1, or 2 and the combined number of t, u and v is 2. This color diffusion transfer photographic element enables to obtain stable dye images of clear and color tone.

Description

SS~9 1 ~his invention relates to a ~olor diffusion transfer process and a photographic element to be used in the process. Particularly, the invention is concerned with a color diffusion transfer process using a photo-graphic element containing a novel color image forming material.
; There are various color diffusion transfer processes which are different in how color image fol~nlng materials release di~fusible dyes during development of silver halide, Among the prooesses~ a first typical method, in which the so-called dye developing agent being a compound having both a dye moiety and a silver halide developing moiety in the molecule is employed as a color forming material and oxidized with silver halide to show a change in its diffusibility, is disclosed in ! various patents such as British Patent 804,971.
In a method using the above-mentioned dye developing agent~ the dye developing agent which is ; sub~ected to diffuslon transfer to an image receivi~g layer has a silver halide developing moiety and abounds in reactivity. Therefore, resulting dye images often suffer from color ~ontamination, a color tone change or the like due to such reaction as air oxidation after the diffusion transfer.
~ second typical method is such as using a color image formin~ material releasing diffusible dyes f `
due to a coupling reaction or further due to a ring closure reaction between a silver halide color developing agent oxidized by silver halide and the color image forming materialO

.' ~

S5~79~

1 This met~od for color diffusion transfer process is disclosed in, for example, U.S. Patents 3,227,550, 3,443,941 and 3,227,551 and British Patent 904,365.
In the above-mentioned second method, i~ is essential to use a silver halide color developing a~ent as which ordinarily p-phenylenediamine type compounds - are used.
The above-mentioned p-phenylenediamine type compound~ in many cases give lmdesirable effects on dye images because their oxidation products generally cause color contamination. ~urther, the p-phenylenediamine type compound~ have such defects as are apt to cause dermatitis in the practical use thereof.
In addition to the above-mentioned ~irst and second methods, there is a third typical method in which employed is a nondiffusible color image fo~ming material to be subjected to such reaction as an oxidation-reduction reaction with an oxidation product of a silver halide developing agent, and an oxidation reaction directly with silver halide, thereby to release diffusible dyes or their preoursors due to hydrolysis by alkali or due to a ring closure reaction. This color image forming material is called a dye releasing redox comp~und whi~h will be hereafter ca~lled as a DRR compound.
This method for color diffusion transfer ~' proce~s is disclosed 9 for ex~mple, in U.S Patents 3,698,897, 3,725,0629 3,728,113, 3,2~5,7899 3,443,9~9 and 3,705,035, U.S.B. 351,6739 ~rench Pa-tent 2,284,140, Japanese ~aid-open-to-public Patent Publication Nos~
33,826/73, 118,723/75, 2,327/72, 104j343/76, 113,624/76 IL557~

1 and 64,436/74, Japanese Patent Publication No. 39,165/73, Japanese Patent Application Nos, 78,057~76 and 125,357/76, and Research Disclosures 15,157/76 and 15,654/77 ~
The above-mentioned third method is more 5 advantageous than the above-mentioned ~irs-t and second methods in the respect that dye images of little color cont~nination may be obtained because what is tr~lsferred to an image receiving layer comprises a dye moiety or a dye precursor moiety but does not comprise a silver halide developing moiety and because it is not essential to use a color developing agent such as p-phenylenediamine type compounds and it is preferably possible to use a black-and-white silver halide developing agent~
In the above-mentioned so-called DRR method, a photographic element comprising a photosensitive element having therein a light sensitive silver halide emulsion layer and the so-oalled DRR compound associated therewith is exposed to form latent images in sil~er ;
halide grains in the emulsion layer and then, processed with an alkaline processing solution. The process~ng may be conducted in -the presence of a silver halide developing agent if desired. In the processing9 the ~`
above-mentioned photosensitive element and an image receiving layer are superposed on each other so that diffusible dyes or their precur~ors released from the above-mentioned nondiffusible DRR compound are diffused by transfer into the image receiving layer to obtain dye images thereon, ~he DRR compounds suitable for this DRR
method have to meet such essenti~l requirements as follows, ~5S7~

1 (a) the compound should easily be dissolved into a hydrophilic colloid, ~b) the transfer efficiency and the transfer speed o-f the dye moiety or its precursor as transferred to the image receiving layer should be high, (c) the dyeability of the dye moie-ty or its precursor transferred to the image receivin~ layer should ~e ~ood, (d) the spectral absorption after the transfer should give preferable color tone, and (e) dye images formed in an image receiving layer should sufficiently be stable.
~ urther, in case of using said DRR compound in combination with a light sensitive silver halide emulsion having spectral sensitivity substantially in the li~ht absorbing region of the DRR co~pound, if the DRR
compound is contained in such layer as placed on the exposure side of the light sensitive silver halide emulsion layer or contained in the light sensitive silver halide emulsion layer, the number of photons absorbed by the silver halide is reduced due to the light absorption by the DRR compound itself to ca.use the desensitization. In order to a.void the desensitization, :~
there is developed the so-called shift type color diffusion transfer process using such DRR compound as temporarily shifted in its light-absorbing spectrum to increase the quantum efficiency at the time of exposure and returning irreversibly the temporarily shifted :`
light-absorbing spectrum to the non-shifted light-absorbing spectrum at -the certain stage after the exposure/ The shift type DRR compounds suitably used 15S7~

1 for the above-mentioned shift type color dif-fusion transfer process have to meet the following essential requirements (f) to ~h) in addition to the above-mentioned requirements (a) to (e)o (f) the compound should have an enough shi~t width ln the light-absorbing spectrum not to impair the sensitivity of the silver halide emulsion, (g) the light-absorbing spectrum should irreversibly return to the non-shifted light-absorbing spectrum swiftly at the certain stage after the exposure, and (h) it should not return to the non-shifted spectrum before the exposure.
As those similar to the non-shifted DRR
compounds used in this invention, there is conventionally known such DRR compound as having an azo dye moiety having a dimethylamino group, an acetamido group or a benzamido group. ~hese compo~mds, however, cannot be said sufficiently to meet all the above-mentioned requirements of (a) to (e~. For example, -the compounds do not show a preferable color tone after the transfer or dye images formed in an image receiving layer is not sufficiently stable.
On the other hand, as a shift type DRR compound9 further, there is known such compounds as having an azo dye moiety containing an acyloxy group therein ~his shift type DRR compound, however, cannot satisfy all the above-mentioned essential requirements of (a) to (h~ in some way or other.
~mong the conventional shift type DRR compounds there is not known such as similar to the shift type DRR

~5~i79 1 compounds used in this invention which compounds have an azo dye moiety and an amino group substituted with ~n aromatic group and an acyl group. Therefore, the object of the present invention lies in providing a novel color diffusion transfer photographic element and the process therefor using a novel color image forming material and particularly in providing a novel color diffusion transfer process using a novel D~R compound. In other words, the object of this inven-tion lies in providing a novel color ~iffusion transfer photographic elemen-t and the process therefor using a novel DRR compound meeting satisfactorily all the above-mentioned requirements of (a) to (e) which the DXR compounds should fulfil. i~ore particularly, the object of this invention is in providing a novel shift type color diffusion transfer photographic element and the process therefor using a novel shift type D~R compound which has as its fundamental structure a novel DRR compound meeting satisfactorily all the above-mentioned requirements of (a) to (e) and which meets satisfactorily all the above-mentioned requirements of (a) to (h).

5i579 1 The other object of the invention lies in obtaining stable dye images of clear a~d color tone by using the above-mentioned color diffusion transer process and elemen-t.
~he above-mentioned objects of this invention :
as well as the other objects which will be made clearer later, may be accomplished by using a color diffusion transfer process which comprises imagewise exposing a photosensitive element comprising at least one light sensitive silver halide emulsion layer and a nondiffusible compound of the following general formula [I~ or ~II].

Formula [I~

[Ml~(Xl)q~Al~ll~ A2\[(X~)S-~ll]p Formula ~II]

Z ~(X2)r-~3 N-A2-N=N-Al~ u -N=N~Al~ ( Xl ) q~ 2 \~ ( x ) A2-N=N-Al . "

A3- / ;

[In the above formulaeo A1 represents an aromatic hydrocarbon group which includes substituted aromatic hydrocarbon, an aromatic heterocyclic group which includes a substituted heterocyclic ring, a nonaromatic heterocyclic active methylene containing group which includes a ~ubst.i.tuted nonaromatic heterocyclic active 1 methylene containing ring, nonaromatic heterocyclic active methine-con-taining group which includes a substituted heterocyclic active methine-containing ring, an aliphatic active methylene~containing group which includes the substituted, an aliphatic active methine-containing group which includes the substituted, or a group of the formula -A4-N=N-A5- (A4 an~ As each represent here aromatic hydrocarbon group, an aromatic heterocyclic group, a nonaromatic heterocyclic active methylene-co~taining group, a nonaromatic heterocyclic active methine-containing group, an aliphatic active methylene containing group or an aliphatic active methine-containing group all of which groups include the substituted as mentioned above) 9 A2 ~nd A3 each represent an aromatic hydrocarbon group or an aromatic heterocyclic group both of which include the substituted9 Ml represents a dye releasable monovalant moie-ty9 M2 represents a dye releasable divalent moiety;
Xl, X2 and X3 each represent a divalent joint group9 Z represents hydrogen or a group of the formula YC0- in which YC0 represents a hydrolyzable group9 m, n and p each represent zero or a positive inte~er and the combined number of m~ n and p is not less than 19 q, r and s each represent zero or 19 and t 9 u and v each represent 0, 1 or 2 and the combined number of t, u and v is 2~, developing the photosensitive element with an alkaline processing solution in the presence of a silver halide developing agent, releasing a diffusible dye from -the 31 l~SS79 1 said compound and carrying out the di-f~usion transfer of the diffusible dye to an image receiving layer corresponding to the imagewise exposure.
Further detailed description will be made below as to the compounds of the above-mentioned general formula ~I~ or ~II]
As to Al, A4 and A5 in the above formula, the aromatic hydrocarbon group includes a benzene group~
a naphthalene group, a phenol group, a naphthol groupg an anilino group, a naphthylamine group9 a diphenylamine group, a monoalkylamine group and a dialkylaniline group.
As the aromatic heterocyclic group, there may be included a pyridine group, a pyrimidine group, a furan group, a thiophene group, a pyrazolone group, a pyrazolobenzimidazole group, a pyrimidazolone group, a 2,4-dihydroxyquinoline group, a methylindole group, an N-ethyloxyindole group, an ~-phenyl-~-anilinoglutacon-imide group, a thioindo~yl group, a cowmaran-3-one group and a l-acyl-3-oxoindoline group. As the nonaromatic heterocyclic or aliphatic, active methylene- or methine-containing group, there may be included a 3-phenylisoxa-zole-5-one group, a 2,4-dioxochroman group, a 1,3-indanedione group, a 1,3~cyclohexanedione group, a benzoylacetanilide group, a 2-(2'-cyanoaoetyl)-coumarone group, a pivaloylacetanilide group, a p-nitrophenyl acetic ester group and an ~-cyanoacetophenone group.
The aromatic hydrocarbon groups, aromatic heterocyclic groups and nonaromatic or aliphatic active methylene- or methine~containing groups include those substituted further with other substltuents. As these S~

1 substituents, there may be various groups such as alkyl groups, aromatic hydrocarbon groups, alkyloxy groups, aryloxy groups, halogen, .nitro, cyano 9 amino,. acylamino groups, alkylamino groups~ arylamino groups, aeyl groups, ac~loxy groups 9 aralkyl groups 9 hyarOxyl9 carbamoyl groups, alkylcarbamoyl groups, arylcarbamoyl groups, sulfamoyl groups, alkylsulfamoyl groups9 arylsulfamoyl groups, amido groups, sulfonamido groups, carboxyl, sulfo~ halogen-substituted alkyls 9 alkylsulfonyl groups, arylsulfonyl groups, carboxylate groups, alkylearbonyl groups and arylearbonyl groups and combi.nation groups of the above-mentioned groups.
Among the groups as represented by A1, suoh groups as an aromatic hydrocarbon group and an aromatie heterccyclic group are preferred in this invention and those which show the most preferable effect in the process of this invention are such group as a benzene group or a naphthalene group. A is an (m-~l)-valent group in formula ~I~ 9 a divalent group in the brackets having an appendix t in formula ~II), and a monovalent group in the brackets having an appendix u or v in formula ~ or example, therefore, ~hen A is mono-valent, the benzene group is a phenyl group while the naphthalene group is a naphthyl group. When A is divalent~
the benzene group is a phenylene group ~hile the n~phthalene group is a naphthylene group.
With respect to A2 and A3 in formulas ~I~ and ~ , the aromatic hydrocarbon group include~s a benzene group and a naphthalene group as in the case of Al. As ~0 the aromatic heterocyclic group, the-re m~y be included .. .

5~79 1 a pyridine group, a pyrimidine group, a furan ~roup, a thiophene group, a pyrazolone group, a pyrazolobenzimida~ole group, a pyrimidazolone group, a quinoline group and an indole group. ~hese aroma-tic hydrocarbon groups or aromatic heteroc~clic groups include those substi-tuted with one or more of various groups The substituents showing preferable effects in this invention may include alkyl groups, aromatic hydrocarbon groups, alkyloxy groups, aryloxy groups, halogen, nitro7 cyano, amino9 acylamino groups, alkylamino groups1 arylamino groups 9 acyl groups, acyloxy groups, aralkyl groups, hydroxyl, carbamoyl groups, alkylcarbamoyl groups, arylcarbamoyl groups, sulfamoyl groups, alkylsulfamoyl groups, arylsulfamoyl groups, amido groups, sulfonamide groups, carboxyl groupS,sulfo, halogen-substituted alkyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxylate groups, alkylcarbonyl groups and arylcarbonyl groups and combination groups of these groupsO
A2 is (p+2) valent in formula ~I~ while A2 is divalent in the bracket having a~ appendix t or u in formula LII~ Moreover, A2 is tri-valent in the brackets having an appendix v in formula ~ O On the other hand, A3 is (n~ valent in formula [I~ while A3 is monov~lent in the brackets having an appendix t or v in formula In addition, A3 is divalent in the brackets having an appendix u in formula LII].
Among the above-men+ioned groups represented by A2 and A3, -those having particularly preferable effects in carrying out the process of the present invention are aromatic hydrocarbon groups.

_ 12 -SS7S~

1 Further, the group of the for~ula -N-A~ is directly bonded at the proper position on the nucleus which -~orms an aromatic ring of the aromatic groups for A2, and preferably bonded at the position adjacent to a position to which the -N=N- is attached.
Ml represents a dye releasable monovalent moiety which is the so-called carrier moiety which releases diffusihle dyes from the compound of the above-mentioned formula tI~ as a function of oxidation under alkaline conditions, particularly at a hydroxidion concentration of 10-5 to 2 mole/l.
As a typical example of the Ml moiety of the D~R compound of the general formula ~I~ used preferably in this invention, there may be included those having the following general formula ~III] to rXII~Jo General Formula Q ~

~IHS02- ~' In the above formulao Q represents a nonmetallic atom grouping necessdry to form a 6-membered aromatic ring, which includes a fused ring, preferably such as a benzene ring or a 10-membered aromatic ring preferably like a naphthalene ring and a quinoline ring. The 6-membered aromatic ring includes those substituted with such as halogen, a lower alkyl ~roup or a lower alkyloxy group;
represents an organic ballast group making immovable , . ~
, ` l~lSS7~

l and nondiffusible the compound o-f the general formula rI~
having the group of the general formula [IIIJ as Ml~
under the alkaline conditions preferably at the hydroxidion concentration of lO 5 to 2 mole/l, As the organic ballast group, there may be included long chain alkyl groups, aromatic groups such as benzene type or naphthalene type, or long chain alkyl groups or aromatic groups which are bonded with one end of suita~le divalent groups ` such as the group represented by -Xl- in the above general formula rI~ or [II~ and which -Xl- will be , described below more particularly. As the pre~erable examples of the organic ballast group represented by B
in the compound of the general formula ~I~ relating to this invention, there may be included substituted or unsubstituted C8-22 alkyl groups. Similarly, there may be included the alkyl groups which include~ those substituted with a C8-22 alkyloxy group or the like at the terminal end o-f a divalent group comprising any 1l combination of such groups -C-, -N-, -CH2-, phenylene group, -0- and -S02- and the groups ~hich are bonded with a phenyl group or a naphthyl group including those substituted with an alkyl group, an alkyloxy group or the like.
D represents -ORl or -NHR2. Herein R
represents hydrogen or a hydrolyzable group which cleaves the linkage between Rl and 0 pre-ferably under a hydroxidion concentration of lO 5 to 2 mole/l and pre-ferably represents O O -Il 11 hydrogen or a group of the formula -CR3 or -C-0-R3 ~5~

1 Herein, R3 represents an alkyl group, particularly a Cl-18 alkyl group Like a methyl, ethyl or propyl group, a halogen-substi-tuted C1-18 alkyl group like a chloromethyl or tri-~luoromethyl group, or a substituted or unsubstituted phenyl group. And R2 represents hydro~en, a Cl-22 alkyl group or a hydrolyzable group which cleaves -the linkag~e between R2 and N preferably under a hydroxidion concentration of 10-5 to 2 mole/l, The preferable hydrolyzable groups are those having a group of the formula -CR4, -S02R5 or -SOR5. Herein R4 represents a Cl-4 alkyl group like a methyl group, a halogen-substituted alkyl group like a mono-, di- or tri-chloromethyl or trifluoromethyl group, an alkylcarbonyl group like an acetyl group, an alkyloxy group, a substituted phenyl group like a nitrophenyl or cyanophenyl group, a phenyloxy group including those substituted with a lower alkyl group or halogen 9 a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyle-thoxy group or an arylsulfonylethoxy group. R5 represents a substituted or unsubstituted alkyl or aryl group.
~urther, X is 0, 1 or 2, preferably 1 or 2.
Except for the case that R2 is along chain alkyl group such as a ~ ~ C22 alkyl group in the formula -NHR2 into D, X is 1 or 2, preferably 1. ~ ;
~he preferable examples of the M1 moiety of the above general formula ~III] in this invention may be as followsO

lS~;7 1] OH

) 3lcl5~

[III-2~ '~H2 ~b (n)H31C15/~ . .. ..
NHSO2- :
LIII 3J I 12~25(n) [III-4~ HNC2H5 d~ , ( )C8H17/~ '`

~III-5] 4 9 ( ( n )H ~jl C15 : ~
~s2 ~III-6] OH C5H11(t) ~Co~(C~2),50~C5~11(t) ~III-7] HNC12H25(n) -- 16 - ~

11557g 8] OH

NHC18H37(n) N~SO2 [III-9~ OH
CONH~

~ OC14H29(n) [III-10] OH C5~t ) ~ CON~I(CH2)40~ C5Hll(t) NHS02- ~ ~, HNC12H25 ( n ) NHS02 ~' ' `rIII-12] HNS2C16H33(n) ~ OC2H5 H5C20 1 ~, ~SO2-13] HNCO~
~"~OC2~5 .; . . . ~ .

-- 1 7 -- . .

1 General ~ormula [I~

ORl Q ~ L-(B) ORl :

In the above formula, B, Rl~ Q and x are as explained before and ~ represen~s -SO2-, -S- or -O-, ~he preferable examples of the ~l moiety having the general formula [IV~ in this inven-tion may be as follows~

rIV-l] OH
~ Cl ( ) 31 15 ~ S2-OX ::~

~IV-2~ OH
~ "
( ) 31 15~ SQ2 OH

~IV-3~ OH
(n)~133C16~3/ 2 ;

OH

.

~ - 18 ~

5S7~

rIV-4] OX
Cl~ O-( ) 15 31 ~\Cl OH

rIV-s ] OH
Cl~ Cl (n)C15~31~\ O-OH , rIV-6]OH
~Cl ~:

(n)C 5~ ~o_ ~ -0~ ~;

[IV-7 ]o~
Cl~O-(n)C18H37/~Cl OH

[IV-8~OH
(n)C H ~l ~O-Cl/~\Cl OH

[IV-9]OH `: " ""
(n)C8H17~0-Cl 8 17( ) OH

- 19 - ~ ;

~ ;5~

[IV~10] OH
(n) ~ O- .
OX ~ : :

[IV. 11~ OE
(n) 15H31\~
~0- . "' OX

1 General Formula ~V~

OH
R6 \~ C~2-G- , R
Rg In the above formula. R6 represents hydrogen, an amino group, an alkyl group or an aryl group; R7 and ~ ;~
Rg each represent hydrogen, an alkyl group or an aryl group; R8 r~presents hydrogen, hydroxyl9 an alkyl group or an aryl group but, when R6 is a hydrogen atom, an alkyl group or an aryl group, R8 is hydroxyl 9 and G
represents the group of the formula ~ An~, S ~ An~, S' or NSO2 (herein, L~lG and R'10 each 10 ' represent an alkyl group or an aryl group, and Rlo and R'lo, together with a ~ atom, may form a divalent pyridinium group or a divalent piperazine group, and An~
represents an acidic anion)~

-- ~0 --1~5S79 1 It is preferable that one or two members ~mong R6, R7, R8 and Rg are a group represented by B in the above-mentioned general formula ~III]~
~he examples of the Ml moie-ty ha~ing the above general formula [~ may be as followso ~V-l] OH I 3

2 1 OH B~3 rV-2] OH f 3 C8H17~ C~2-1$3;
OH Br~) [V-3~ OH I 3 CH3 fH3 ~CH2 Nq~) CH3-C-cH2-c ~ 3 `;

CH3 CH3 OH C1~3 , ~V-4] OH CH
, ~a~2-~0-OH B~

[V-5] OH
~ C~2~
( ) 18 37 O~ Cl~

55~7~

~V-6~ OH

f~r CH2-~N~, ( ) 14 29 Cl(3 OH

~V-7~ OH , ~1 CH2 ~N~
(n)C12H25/~ Cl(3 OH

[V~]f ~ f 3 CH -~N~
CH3-CI-CH2-Cl ~ ;
C~3 CH3 OH Cl~

[V-9] OH
~"~CH2~

) 10 21 OH Cl(3 ~V-10] OH I 3 1 3 f 3 f~--CH ~N N-CH3-C~CH2-C~, 1l 2 , General ~ormula ~VI~
D~
( B )~

~q Rll ' -" 311~5iS~7~

1 In the above formula, B and B', Q and Q', and x and x' are as explained be:Eore; ~' represents -C- or -SO2- 9 Rll represents hydrogen or an alkyl group~ .
D' r0presen~Gs hydrogen, hydroxyl, an acyloxy group or ;~

the group of the formula ~< 129 and D" represents hydroxyl, an acyloxy or the group of the formula N <

(wherein, R12 and R13 each represent hydrogen, an acyl group or a hydrocarbon group).
The examples of the Ml moiety having the above general formula ~VI~ may be as follows~

[VI-l~ O
-N--S-NH H O

25C12~ C ~ ~ CH3 ~VI-2~ OH o H

~ O ~:~
-N-S
H o 5S~7~

~VI-3]CH
~ .
NH O
¢ ~ Dll~l `:
O

12H25 CH3 :

[VI-4~ OH O
H7C ~ CH2CH2-C-N~l-Cl2H25 H ~;C/~
NH O
DIHS_ O ~ ~.

[VI-5 ] OH
CH30-¢~CH2CH2CNHC12H25 NH O
~NHC-~VI-6~ OH
COOH

NH

~ , ;.
NH
C=O

~L~15~79 , ~ :
' ~

~VI-7 ] OH

1~ . :
f~ NH~2 NH
C=O . ,' ' (1H2 )16CH3 [VI~1 H I H
~CH2-CH2-c-M-(d~2)ll 3 ~H
~HSO2- .

[~-9~ OH O H
CH2-CH2-C-~-(CH2317 3 ~NE~2- ~

General Formula ~JII] ~ -"R14 :~ ' B )x ~ C=N-NH- ( L ' )y~
Rl 5 5S7~9 1 In the above formulao R14 represents hydrogen, an alkyl group, an aralkyl group or an amino groups and R15 represents an alkyl group, an aralkyl group, an aryl group, an acyl group or an amino group, and R14 and R~5 may be bonded with each other to form a hydrocarbon ring or a heterocyclic ring9 ~' represents a group of the O
formula -C- or -SO2-9 y is zero or 19 and, B and x ~re as explained before.
r~he examples of the Ml moiety having the above general formula ~VII] may be as follows.

[VII-1] ~02 ~ ~=C )~ 16 ( IH2)3 so ~ .
LVII-2] S
-S02-I7H--N=C )~ 12X25 N
(fH2)3 LVII 3] D~
~02-~X-N=CH ~ C16~33 ~VII-4] -SO2~ -N=CH~

~1~5579 [VII-51 S
-S02~ N=C~ ~ 3 C16~33 ~VII-6~
S02-NH-N=f--6~ C12H25 CH3 : ``

[VII-7 -S02-NH-N=f -C17H35 [VII-8 -S02-NH-N=CH-C6H13 ~VII-9] . S
-SO -~X-~ ~q ~N/~S03H

~VII-10]
N
f=N-NH-S02-¦¦ H ~ ~;
C~H2 C N~
fH-C16H31 ~ ,.
C=O , , OH

7 -:

.

SS7~ , ~VII 11~ C117H35 -S02~ N~
(1~2)3 So~H

General Formula LVIII]
) y~ lCI -MH-I~I-S 02-B
w General Formula [IX~
B-(~ )y~C~NH~NH~S02~
W

1 In the above two formulaeO B is as explained before; ~"'represents a group of the formula -O-, -S-, ' 2 , CONR16- or -S02NR16- (In the ~ormulae 9 R16 represents hydrogen or an alkyl group.); W representg oxygen, sulfur or an imino group; and y is zero or 1.
- The examples of the Ml moiety in the above formulae ~VIII~ and [IX] may be as follows rVIII-l]
ON~ H-S02 C17H35(n) ~VIII-2~ -CON~NX-S02~ 15 31 ( ~IX-l~
2 ~H-NX-CO-C15X31 (n) - ~lS~i7~

~IY~-2]

[IX-~ ~02-NH-NECO-O-Cl8H37(n) ~IX-4] ~2 ~E-NH-11-al,~35(n) NH

l General Formula Z'-C-~H-NH~O -B
~(~"')y~ ¦¦ 2 General Formula [XI]
Z~-C-NH-NH~02-B-(L"') In the above two formulaeo B, ~"'and y ; are as explained before9 and, Zl represents a nonmetallic atom group necessary to form together with a carbon atom or a nitrogen atom a 5- or 6-membered, non-condensed or condensed heterocyclic ringO
The examples o-f the Ml moiety having the above ~:
general for~lulae ~X~ and ~XI~ may be as followso 1', LXI-1] ~ -(n)C12H25-EN ~
N ~-- NENH~O -H03S-CH2CH2-~H

~ -- 29 - ~

~XI_2~ N
3SC~2C~2~HCO~ ~NHNH~O2-~ N NHC12 25(n) LXI-3~ (n)C12H25NX~O2 ¢~ /~NHNH~O2 1 General ~ormula ~XII]

,~ Q "~
B - C=D"' ~ Rl8 In the above formula, B is as defined before.
D"'is oxygen or a group of the formula =NR17 (where, R17 represents hydroxyl or an amino group which includes the substituted) and, particularly when D"'is -NR17, the representative R~7 is chose in the group of the ~ormula~C=N-R17 which is formed by carrying out the dehydr~tion reaction of the carbonyl reagent H2~-R17 with a keton-containing group.
As this H2N-R17 compound, there may be included, for example, hydroxylamines, hydrazines, semicarbazides and thiosemicarbazides. More particularly, the hydrazines may include hydrazine, phenylhydrazi~e 7 subs-tituted phenyl hydrazine having on its phenyl group a substituent such as an aryl group9 an alkoxy group, a carboalkoxy group or halogen, and isonicotinic acid S57~ ~

1 hydrazine. ~nd the semicarbazides may include phenyl-semicarbazide and substituted phenyl semiearbazide having on the phenyl group a substituent such as an alkyl group, an alko~ group~ a ca~bo~lkoxy group or halogen and the thiosemicarbazides may also include various derivatives thereof as the semicarbazide.
Q" in the formula ls a saturated or unsaturated 5-, 6 or 7-membered nonaromatic hydrocarbon ring and may inelude as its typical example, for example, cyclo-pentanone, cyclohexanone 9 cyclohexenone, cyclopentanone,cycloheptanone and cycloheptenone.
~ urther9 these 5-7 membered nonaromatic hydrocarbon rings includes a condensed ring fused with another ring at their suitable positions.
15 This partner ring -~or condensation may include ;
various rings, whether they have aromaticity or not or whichever they are hydrocarbon rings or heterocyclic rings, but in this invention more pre-ferable is a ring formed by fusing the above-mentioned 5-7 membered nonaromatic hydrocarbon ring with benzene such as indanone, benzocyclohexenone or benzocycloheptenone.
~ he above-mentioned 5 to 7-membered nonaromatic hydrocarbon ring or the above-mentioned condensed ring may be having one or more substituents such as an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfo1lyl group, an arylsulfonyl group, halo~en, nitro9 amino, an alkylamino group, an arylamino group, an amido group, an alkylamido group, an arylamido group, 7~

1 cyano, an alkylmercapto group or an alkyloxycarbonyl group.
Rl~ represents hydrogen or halogen like fluorine9 chlorine or bromine.
The examples of the Ml moiety having the above general formula ~II] may be as follows~

rXII~
(t)C5H

NHCOCH20 ~ (t)C5H

~XII-2~
(n)C12~25~0~rl01~02~

[XII-3 (n)C16~3~~2 ~ ~2 . O
. . .

~ - 32 -SS'7~

~XII-4]

(n)C12H25-NHS2~ H ¦
~\NHS0 O

~XII-5 ~

(n)CI2H25CONH~ W NHS02 O ~,"

[XII~6~
~1 ' ' '.~
(n)ClOH21~/\~HS0 O

1 General Formula [XII'~
OR
~ S2-G~

Gm-l : ~.
In the above formula, G represents an aroma-tic ring directly fused to the benæene nucleus to form a naphthalene nucleus9 m and n each are 1 or 2 and different from each other9 Rl and ~ each are defined before.
~ he examples of the ~ moiety having the above general formula ~XII'~ may be as followsO

lSS~

OE ~¢~ OH

C-NH(CH2)40~3 C H -t CrHll t C14H29 n rl~ls2- NHS2 OH ~\~

C18H37-n S02NH( CH2 )4-O~ C5Hll-t C5Hll- t . ,~

NH$02~ 02 18 37 ~ OH
So2NHCH2CII-o~3 5 11 C5Hll-t NHS02 N~S2~

~¢~5C18H37-n ~li `;r OH
So2NH~

~ISO2- C14H29 n D\,~o~
~,i~/l S02Cl~H37-n NH~16H33-n ~¢~IIH802 1~" ~CH

S2N'(C12H25-n)^

. .

~L55'?'9 1 General Formula CXII"] :

ORl Xn $~ ~2 OR

In the above-formula, R represents an a.lkyl group or an aromatic hydrocarbon group9 Rl is as defined before; X is a monovalent group or an atomic group to 5 form, together with the -OR group, a condensed ring fused : ~:
to the benæene nucleus, the ring not being an aroma~ic hydrocarbon ring9 and n is 1, 2 or 3, provided that the combined carbon number of Xn and R is not less than 8, further provided that a ~lurality o-f Xs if present may be different, and still further provided that X is an electron-donor group when n is 1 while at leas-t one of a plurality of Xs is an electron-donOr group when n is 2 or 3.
'~ypical examples for the -OR group is an acyloxy group such as a propionyloxy group and an acetoxyl group in addilion to hydroxyl~ ;
The examples of the M1 moie-ty having the above ; general formula ~XII"] may be as followso ~`
. '.
OH O~
~HSO2 ,~NHSO2~ :

. ~ OE OH ;-~

~C31'6!'1~ C15~

~ 35 ~

.
55~7g o~ o~ . ;.
,,~N~IS02- ClX~ ~o~-C~I3 3 C16H33 Oal8~I37 OH So2-~H3 ~ ~02- N~ CH3 C~[3~(C~2C~2C~27~t3C~3 ~' .11~ ~

CH~ CH3 OH ¦ 3 1 3 CH3-C-CH2-f ~ ~ 2- CH3-7-CH2-C ~ ~2-

3 3 C6Hl3 CH3 CH3 0 ~ 3 . CH3 CH~
:, 1 In the above-mentioned for~ula [II~, ~s defined before M2 is a divalent dye releasable moiety which is the so-called carrier moiety which releases ;~
diffusible dyes from the compound of the general ::
formula ~ as a function of oxidation under alkaline conditions9 preferably at a hydroxidion concentration :
of 10-5 to 2 mole/l.
The M2 moiety of the compound of the above general formula ~ used advantageously in this invention may include such as having the following general formula ~XIII~o ~SS'7~

1 General ~`or~ula ~XIII]~
-~o2~ Ar-~H-so2-In the above formula Ar represents an aromatic hydrocarbon group which includes those substituted with an alkyl group9 halo~en or an alkyloxy group, particularly preferably with an alkyloxy group, provided that the two l~H groups are connected through 1-4 combinations of the two carbon atoms in the aromatic hydrocarbon group.
The examples of the M2 moiety having the general formu a [XIII~ may include as follows: ~

, , [XIII-l] ~ NHS02 [XIII-2~ -S2~H ~ ~ - ~ISO -[XIII-3 ~02NH~ N~IS02 - ~7 - .

rXIII--4~ 2 5 ~ :
~2~2- ,`

~XIII-5] C4Hg~n) -S02NH~ NHS02-(n)C4HgO

[XIII-6~ 12H25(~) :
~02-~2~

(n)~12H25 ~XIII-7~
~o2NH~02'' :~

1While the Ml and M2 moietles are explained above in detail, the most preferable effect may be obtained in this invention in the case that the Ml moiety in the compound of the general formula ~I~ has ~ :
formula ~III~.
In the above general formulae ~I~ and ~ 9 Xl, X2 and X3 each represent a d~valent joint group.
The preferable Xl, X2 and X3 in this invention are a divalent joint group being one member selected from, or any linear combination of two or more members belonging to7 the group consisting of -O-, -$-, ~5S~

2-~ -S0-, -N-, -~R20R2~ CR20=~l'21 above formul.ae, R19 represents hydrogen, an alkyl group or an aromatic hydrocarbon group! and R20 and R2l each represent hydrogen, halogen, an alkyl group or an aromatic hydrocarbon group), substituted or unsubstituted aromatic divalent groups aMd the groups of the following formulae- :
(X' ) /(X )a\R20 R~,(X )a\R20 \X"/ \X"/ aMd ~C\X''/C~ "

(In these above three formulae~ X' and ~" each represen-t a divalent group being one member selected from, or any combination of 2 4 members belonging to, the group Il .
consisting of -0-, -~ C-, -S02-, -S0- aMd the above-llgmentioned groups of the following formulae -N-, -CR20R~l-and -~R20=aR2l~; a is zero or 19 and, (X')a and X"
-together with N and/or C ~orm as a whole a 5 or 6-membered ring.) Further, the more preferable case in this invention i9 when Xl, X2 and X3 are the groups of the ~ :
formula -El~Jl)b (~2)c ~( N )d J2t N

In this ~ormulao El and E2 each represent, a C1-8 alkylene group or a phenyl_ne group and these alkylene aMd phenylene groups include those substituted with halogen, .:
an alkyl group or an aromatic hydrocarbon group 9 R2z and _ ~9 _ 5~i79 1 R22' each represent hydrogen, a Cl-8 alkyl group or a ~6-1~ aromatic hydrocarbon group such as a phenylene group, a tolylene group or a naphthylene groupy O O O O
Il 11 11 11 ;
Jl represents -0-, -S-9 -C ~ -C 0-9 -0~ -OC-O-~
O O
~ H ~ H
-NC-, CN-, -NS~2-, -S02N-, -S0-, -S02-, a al-8 alkylene group including alkylene substituted with halogen, or an unsubstituted or substituted phenylene groupp J2 O :.
represents -S02- or -C-9 b and c each are zero or 1 but~
when b is 1, c is 1 and, when b is zero, c is zero or 1 (provided, when c is 1, the total C number of Bl and ~2 is less than 15)9 and~ d, e and f each are zero or 1 and the total of d and e is 1.
In the above general formulaa ~I~ and the YC0-group for Z represents a group hydroly~able .
preferably at a hydroxidion concentration of 10 5 to 2 mole/l in order to be cleaved off -from the bonding with the nitro~en and in this case the compound of the : general formula [I~ or ~ is the so-called shift type : :
DRR compoundO As the Y in the g~oup YC0 having a preferable effect in this invention, there may be included C1~5 alkyl groups such as a methyl group7 ~n.
ethyl group9 a propyl group9 an isopropyl. group9 C1~5 alkyl substituted with halogen a-t the ~ or ~-position such as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromometh~l9 tri~luoro-methyl, ~-bromoethyl, ~-bromobutyl, pen-tafluoroethyl and - d bromoisopropyl9 C1-5 alkyl substi-tuted at the ~ or ~-~.

-- ~0 --lgL~LS5'7~39 1 position with a substituted or unsuhstituted aryloxy group or a substituted or unsubstituted al-5 alkyloxy group such as methoxymethyl, propoxymethyl, phenoxymethyl and ~-phenoxyethyl9 Cl~-5 alkyl substituted at the ~- or ~-position with hydroxyl such as hydroxymethyl, As suchthe Y, there may further be included a vinyl group substituted with substituted or unsubstituted Cl-5 alkyl groups or aryl groups such as ~methylvinyl and ~-phenylvinyl; aryl groups having 1-3 substituents such as halogen, nitro, cyano and trifluoromethyl9 or the group of the formula -OR23 or -C-OR24 (in which R23 represents a substituted or unsubstituted, Cl-5 alkyl or phenyl group9 and, R24 represents such group as represented by R23 or hydrogen. As the substituent in the alkyl groups, Cl-5 alkylsulfonyl groups? amido groups, hydroxy, carboxyl, alkoxy groups and h(~logen are preferabls. And as the substituent in -the phenyl groups, halogen, nitro, cyano, -trifluoromethyl and 20 methyl are preferable and it is preferab]e that 1-3 -substituents are presented in the phenyl group.) The examples for -OR23 are ethoxy ~-methylsulfonylethoxy9 phenyloxy, ~-chlorophenyloxy. The examples for `

-~-OR24 are ethoxycarbonyl and carboxylO
~he more preferable in this invention among the groups for Y in the formula YC0-, are Cl-5 alkyl substituted, at the d- or ~-position, with halogen or a I l . ~
group of -the formula -OR23 or a-Q-R24, the most preferable being trifluoromethyl.

S~;79 1 With respect to m, n and p in the before- :
mentioned formula ~I], it is more preferable that m, n and p each are zero or l and the total of m, n and p is l. It is still more preferable either that n and p each are zero and m is 1 or that m and p each are zero and n is l. In addition to this case, when the groups represented by Al, A2 and A3 are aromatic hydrocarbon groups, the best effect may be shown in this invention~
As to t, u and v in the above-mentioned general formula ~ , the best effec-t may be shown when t is 2.
In ~he above-mentioned formulae ~I~ and q, r and s each are zero or 1.
Among the compounds of the general formula ~I~
or ~ as specified in detail? those showing much more preferable effects in this invention are compounds of ths following general formula ~XIV]~

General Formula ~XIV~
R(l) R(2) ~Ml~(Xl)q ~ Al ~ R(3) R(4) (R(5)) In the above formula, Al' represents a substituted or unsubstituted 9 aromatic hydrocarbon or 20 aromatic heterocyclic group. As the substituent on the~ :
aromatic hydrocarbon or the aroma-tic hetero ring, there may be included those described above as the substituents :~

of A2 or A~ in the above general forrnula ~I~. Ml r ~1~ q ; and m each are as defined beforeO R(l), R(2) and R(5) each represen-t hydrogen9 halogen? nitro 9 an alkyl group - ~2 -.. . .

5S~9 1 including halogen-substituted alkyl (for example, trifluoromethyl and chloromethyl), hydrox~yl, a group of the form~a -OCOY' (herein, the Y' ao- in the -OCOY' group represents a hydrolyzable group which cleaves the bondage with an oxygen atom preferably at a hydroxidion concentratio~ of 10 5 to 2 mole/l. The group of ~'C0-having more preferable effects is the group o~ the O O
~ormula R(6) -C- or R(6)-0-C-. In these cases, R(6) represonts a Cl-18 alkyl group including halogen-substituted C1-18 alkyl, a C6-18 phenyl group in¢luding substituted phenyl~, a group of the formula -0~(7) ~wherein, R(7) represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. As the substituent ~n the above-15 mentioned alkyl or aromatic hydrocarbon group, there :~:
may be included alkyl groups, alkyloxy groups, aryloxy groups, hydroxyl, amido group, carboxyl, carbamoyl group, sulfamoyl group, halogen, acyl groups, acyloxy groups 7 alkoxycarbonyl groups, alkoxyoxalyloxy groups and the like The case having more preferable effectsin this in~ention is that R(7) is a substituted or unsubsti.tuted Cl 15 alkyl group; that iS9 that R(7) is an alkyl group such as methyl 9 isobutyl 9 a carboxyalkyl group like ~-carboxyethyl; such alkyl, substituted with a sulfamoyl group, a carbamoyl group or an aromatic hydrocarbon group, as d-phenylcarbamoylethyl or d~
sulfamoylphenylcarbamoylethyl 9 a hydroxyalkyl group like ~-hydroxyethyl 9 an alkoxyalkyl group like methoxyethyl, ethoxyethyl or ethoxyethoxyethyl; a halogen substituted . . .

-~ 1$3~557~

1 alkyl group like chloroethyl7 alkyl substituted with an amido or sulfonamido group 9 or alkyl substituted wi-th a group of the formula o-c-~(6), ~OC-0-R(6), -oaCoR(5) or -C-OR(6) (in the respective formulae, R(6) represents a C1-18 alkyl group, a C6-18 phenyl group including substituted phenyl), for examples, ethoxyoxalyloxyethyl or ethoxycarbonylethyl,acetoxyethyl, and ethoxycarbonyloxy-ethyl~, an amido group, an alkylamido group1 an arylamido group (e.g. benzamido), a carbamoyl group, an alkyl-carbamoyl group, an arylcarbamoyl group, a sul~amoylgroup, an alkylsulfamoyl group, or an arylsulfamoyl group. Further, R(l) and R(2) may be bonded with each other thereby to form a naphthalene nucleus. In this case, X(5) may be bonded with any position of the naphthalene nucleus R(3) and R(4) each represent such group as defined for the above-mentioned R(l), R(2) and R(5) or, -the group of the formula -N-A3 ~ (X2)r-Ml]n~ In formula, A3 is as defined before; that is, a substituted `
or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group?
preferably a substituted or unsubstituted aromatic hydro-carbon group~ Ml, X2, Z', r and n are as defined before.

However, at least either one of R(3) and R(4) is the Z' 25 group of the formula -~T-A~-(X2)r--Ml~ n- -Xl in fornlula [XIV] represen-ts the same as Xl _ ~.4. _ SS~?'9 l in the general formula ~I] 9 that is, a divalent group and the most preferable as X1 is the group of the formula.

R22 R22 ;, l (J1)b-(E2)C ~(~T )d-J2-( N ~ f (The symbols used here are the same as mentioned before.
Finally, w is an integer of l to 5.
While the compounds of the general formula [XIV~ having more preferable effects in this invention have been specified in detail in the preceding description, much more preferable compounds are those wherein either of R(3) or R(4) is the group of the above mentioned Z' formula -~-A3~ (X2)r-Ml]n (The most pre-ferable results are obtained when A3 is a substituted or unsubstituted phenyl groupO) While the other of R(3) and R(4) or at least one among R(l), R(2) and R(5) is hydroxyl or -the group of the above-mentioned formula -OCOY' or ~-oR(7) (The most preferable results are obtained when the o-ther of R(3) and R(4~ is hydroxyl.); Z' is an acyl group containing the before-mentioned ~- or ~position halogen-substituted Cl-5 alkyl or the group o-f the above-mentioned O 00 ``
formula -COR23 or -aC-0-R24 (~he most preferable group is trifluoroacetyl ) 7 and9 the total of m and n is 1.
The typical examples of the compound having the general formula [I] or ~ which may be advantageously I used -for this invention will be shown in the following but it is n~t intended to limit the compou~ds of this ; invention thereto.

5S'7~

(1) CONH(CH2)4-O~ 5 11 NHCOCH2CH2~ N=N ~ OH

b (2) OIIC,~l t CONH( CH2 ) 4-O-~ C5Hll NHSO;,~
NHSO2CH2CH2~N=N~ OH

,:~
(3) :
c~ll t GONH ( CH2 ) 4- ~,3 C5Hll-t NHCoCHoCH2CH24~N=N ~} OH ~ . .

(4) CONII ( CE 2 ) ~- ~ C5111 1-t NHS02 ~CH2C112~N=N~OH ' :,~
I~-COC~3 ' .

S~i7~

( 5 ) C H - t ~CONH(CH2),~-O~c5Hll_t NHSo2~
NHS02~ CH2CH2~ N=N ~OH

(6) ~CONE(Cn2)4-0~5Nll t NHSO2 4 \~
NHCOCH2CH2~ N=N~ OH
COCF3 :' ~Cl (7) .

~¢~CoNN(01~2)4-0~ C5Nll HS2~; ~ / CH3 -NHCOCH2CH2~ N=N~OH
N-COCF

(8) C~;Hll t ~CO~ll(C112)4-0~CS~

NHCOCH2CH2~N=N $~ OH

- ~7 --: - - ` . . -. .

( 9 ) C~ t ~CONH(CH2)4~0 e~C5Hll-t NHS02~ CH2CH3 NHCOCH2C1~2-~ N=N ~--OH ~:
N-COCF
~3Br (10) OH C~l-t ~-coNH(cH2)~ -o - ~ c5Hll NHSO~--~ ,~CII2CH3 N~ICOCH2CH2--~3 N=N--~ OH -N-COCCl_ ~Br ~11) OH C5Hll-t CO~H(CH2)4-0--~ C5Hll-t NHS02~ CH2C~3 NHCOCH2CH2-~N=N~ CH2c~3 N COC~
~3 OH

(12) OHC5Hll-t NH502~
NHCOCH2CH2~ N=N OH
Cl N-COCF
' - -- 48 -- ~
~ `~

. .~

~ss~g (13) C5~ t ~o~ o~

NH$02~ N=N OH
Cl N\COCP3 ~ .
(14) C ~ t CONH(CH2)4-O ~ ~ C5Hll 2~
N=N ~ OH `:
i~-COC~3 (15) C5llll-t ~_CONH(C~z)4-0~c5Hll-t NXS2 ~ ~ Z 3 NHCOCH2CM2- ~ N=N- ~ -OH
; .

~ ~ Br (16) OH C5Hll-t CONH(CH2)4-O ~ 5 11 NHS02 ~
SO2NH - ~ N=N ~ -OX
N ~ F

iS7~

(17) OH C~l-t ~CONH(CH2)4-0--~ C5Hll-t IIHCOCH2CHz~ =N--~OEI

N-COCCl ~--CF3 (18) OH C5E~ t ~¢~CONH(CH2)4-0--~3C5Hll t 2~
\~ NHCOCH2CH2~N=N~ OCOCH3 ( 19 ) CONH ( CH2 ) 4-0 ~ C5 NHSo24~ .~ -., MHCOCH2CH2 ~ Il=N-- ~ OCOCH
N~COCHC12 ~Cl - (20) ~ ~3 OH
N-C.OCF3 ~\~ CONH ( CH2 ) ~1 -

5 H11 t - 50 - :

s~

( 21 ) CH2 CH3 OE / OH
--N=N~OCH
~N~ ~/ 3 ~1~ CONH(CH2)4-- :

3 ~ > ¢~ C5Hll t (22)CH3 OIE 5 11 a~E3~ N-W--~7 OCH~ CONlE(clE2)~-O~c5}Ell t O ~ ~ S2 II

NO
2 ~

(23) ~ ::

f~N=N~oCH3 OH C~l-t N~\ ~C/OCE'3 ~CONH(CH2)4-0~ C5H11-t

6 5 ~ ~ SO2WEI

(24) COCH3 CH~;
CH-N=N~ OCH7 OH C5~-t ~\E~ CONH( CH2 ) 4 -O~ c5Hll-t CONIiC6H5 ~F3 CE2CH2CON~

- 51 - :

55'7~
(25 ) ~N=N~ ~; 11 N-COCE'~ OH \' ~¢~CONf(Cif2)4-O~a5Hll $02NEI

i.~2Ç) N=N--~3 N-COCC13 OH G5Hll t GONH( CH2 )4-O ~ C5 (27) N=N--~ C Hll-t N-COCHC12 OH 5,~

NHS~¢~ COIJX ~ CH2 ) 4-O ~ 5 11 $02NH

(28) ~,COII f(Clf2)4-0~CS fll-t 2~ CX3 So2N:~3N=N~oC2H5 Cl 1~5S7~
, (29) OH C ll-t ~CONU(C112)4-0~C5~11-t NHSO2~ ,~,CH3 NHCOCII2CH2--~ N=N~

~3 Cl :
(30) C5~11~t OH
CONH( CH2 ) 4-0~ C5Hll-t , ~3 ;.

(31) C Hll-t ~¢~CON (CE2)4-O~ 5 11 NHS02~ /C2H3' ~NHCOCH2CII2~N=N~
~13 `

:

(32) CH3 N=N~

~H2 N-COC~3 Oll ~1 C II ~-N~S~CON~(CH2)4-0~ 5 11 S2~

~5~79 (33) COIII~(C~2)4-0~C5~11-t NHS02~ N~COCH2CX2--~--N=N~ OCX~;
~Cl (34) C5Hll-t ~

~CONH(CH2)4-0~ C5Hll-t " . ~

NHSO2~ Cl '~S02NH~N=N ~OC H

~ 3Br (55) ~ GO11H(C}l2)4-O~ 5 11 NHSO
~3 N=N~OCH3 H `
ph~N~ ~CC~ OH

~3~ ~coNN(cN2)4-o ~C5Hll t -- 54 ~ ~

557~

(37) C ~1 -t OH
~CONH(CH2)~ 0~ ~ C51Ill-t NHSO2~ CH3 ~S02NH--e~3N._N~
N-COCE3 l~CON~I(CH ) o 5 11 t ~2~
~2NH C5Hll-t (38) ~

~N=N~ OH 5 11 N02 A~COC~3 ~ CONH(CH2)4-O~c5 ~NHSO~

~ S02NH
(39) C Hll-t ~¢~CONH(CHz)4-O~ 5 11 NHSO2~ ~ Cl `.
NHSO2~N=II~ OCH3 N~F3 . i ~Cl (40) C5Hll-t coNH(cH2)4-o ~ C5Hll-t . ~NHCOCH2CH2~ ~H3 C~;

ss~

(41) C ~ l-t ~¢~CONH(CH2)4 -0~C5Hll ., NHCOCH2CH2- ~ N=N ~ OCH3 2 3 .
'~

t42) OH 5 11 ~CONH(CH2)4-0~c5xll-t NHS2 4 ~ ~ OH
NHCOCli2CH2- ~ N=N ~

OHC~5Hll-t ~43) ~ ~ ,CONH(C1~2)4-O ~ 5 11 CH3 ~ SO2NH
N=N-/ ~ OCH2CONH

~ F3 (44) C~ ~ Cll2-N-Cll~ ~ ~ C'~3 ( 3)3 2 1 OH . 3 ~ ~ EEal CH3 Cl-CE~ `

.

(45) ~ :
OH

31 15 ~ 0z- ~ CH2CH2 ~ M=N ~ OH
: N-COCF~

(46) OH
n 131C15 ~ ~ CH2CH2 ~ N=N ~ OH

Cl ~ Cl N-COCF3 0~

(47) OH
H2cH2coNHcl2H25 NHS02 ~ CH2CH2 ~ N=N ~ OH
- N~COCF3 e~ ~

(48) -OCH
33 16 S02NI~ ~ ~
OCH3 NHCOCH2CH2 ~ -N=N ~ OH
N\COCF3 ~ ;
~) '' s~

(49) n-H3~jC16-0~ \C=N-NHSO24~ ~ ' `` ;

(CHz)3 ~NHCoCH2CH2~3 N-cOCII
SO3H ~ 3 ( 50) ~ ~ -n-H29cl4-NHco-N~lNlI-so2 ~
NXCOCH2CH2~ N=N--~ OII

_~ (51) 31 15 ~ SO2NHNHSO
NHCOCX2C~12-~ N=N~
N~ID3 (52) .
O
~I=N4~ OII 5 11 IIC~ Y ~ co~ (c~l~)4-o~c5 CH2CI12CONx ,' -~

.
;'' ~ SiS79 (53) OH 5Hll t CNH(CH2)4-0~'5~11 t NHS02~
~N=N~ :
~9 3 ~<

(54) OEI

e~ ~ n-H31 Cl 5 `~

~NEICO--(55) ~¢~CONHC18H37 ~) N=N~ OH

(56~ fOCF3 ` C12H25-n '`

N=N~ OH
- N~F3 ~:.

`- 59- .

5~

(57) OH \5 11 CoNlI ( GH2 ) q~-o -~c5~ t ' ' Cl ~-S021~H . :
~N=N-~ OCH2CONH

~3 -:

(5~3) \5 11 CONI-I(C~2)~1-0~C5 N=N--~ OCH CONH~ 2 N- COCP~;

::
Cl N~(c~l2)~-o~o5 --NHCOCH2CH2--~
N--N--~ OII
~OCE'~
~'.

Cl ~60)C51Ill-t NHCOCH20 ~ C5Hll ~'NHS02~--N=N--~3 OH
N-COCF~;

_ ~0 -.S57g (61) OH C5Hll t CONH( CH2 ) 4-O ~ C5H

NHSO 2-~
\~(NHCOCH2CH2~ N=N~ OH
NH

(62) 0~1 C~ t ~¢~ CONII(CH2)4-O~C!5Hll-t NHSO2~
02CH2C 2~N IT~OH
HN ~
è~s - ~

( 63 ) OH C5Hll-t ~o~ coNH ( cH2 ) 4-o~ c5 ~ t NHSO2--~ C~3 NHCOCHOCH2CH2~ I`T=N~'~ OH
HN

(64) OX C5~ t CONH(CH2)4-O ~ C5Hll-t 2 ~ J 2 2 ~ N=N ~ OH
HN

7~

(65 ) OH C5Hll-t CONH(CH2)4_o~C5 ~11 t NHSO2~
\~NHSo2~3 CH2CH2--~--N=N ~ OH
HN

(66) C5~ t ~,CONH(CH2)4-O~ C51L~ll t NHSO24~
\~ NHCOCH2CH2~ N=N ~ OH

~Cl (67) 5 11 ~¢~ CONH ( CH2 ) 4- è3 5 11 NHSO2--~ CH~
\=~ NHCOCH2CH2~ N=N~--OH
HN

( 68 ~ C H -t OH 5~11 CONH ( CH2 ) 4-O--~ C5Hl l-t NHS02~` NHCOC I CH ~ Il=N~ OH

~3C~3 - ~2 -1~55'~

(69) OH 5 11 ~¢~ CONH ( CH2 ) 4-O ~C5Hll t NHSO2~ NHCOCH2CH2 ~ N=N ~ OH
HN
?~ Br (70) C5Hll-t ~¢~CONH(CH2)~-0~c5Hll-t NHS02 ~ NHCOCH2CH2 ~ N=N ~ OCE2CH~;
H ~:
~OH

NESO2~ a5 11 t NHCCH2CI~2--~ N=N~ OH :~
Cl H

(72) OH C5Hll t FCONE(C 2)4-o~C5}~1, NIIS02~ N=N OH
Cl HN

~SS~9 ~

(7~) C5~-t ~¢~ CONH ( CH2 ) 4-O ~ C5Hl1- t llH$02~ ~
N=N~ OH
ElN

(74) C5~-t ~CONH(C~I2)4-O~C5Hll-t NHSO --~
2 ~ SO2NH--~ N=N ~ OH ::

HN

~Cl ~75) 5 11 ~, CONH( CH2 )4-~ C5Hll-t NHSO2~ NHCO CE~2CI12~ N=N--~ O CO CE13 HN
~ ' (76 ) OH C5Hll-t ~, CONH(CH2)~!,-0~C5Hll-t' NHSO--~
2 ~NHCOCH2CH2--~ N=N ~ OCOCH3 iiS'7~

C5Hll-t =N~3OH ~ C~ (cH?)4o~ 5 11 ~S02NH

(78) :~
OH CH2C113 Oli 5~ 11 t ~vi~ " l~o ~ OCH3 C~CONH( CH2 ~4---h C:~Hll-t II ~ ~ 2 ~< .

(79) OH 5 11 ~ ~\f~CN~ 2)4-o~ c5~ -t CH3 ~ =N~ OCH3 ~ ~2 ¢D CH2CH2CONH ~ ~, (80) OH C5~Hll CH3 ,~CH3 I CONH(CH2)4.-0~C5Hll-t ~N=N ~ OC~13 O N OH NH
~3 2 C~12CH2CONH ~ .
' sst~

(81) OH C5Hll t f ~ ~,~,CONH(CII2)4-o~c5~ t CH-N=I~ ~ O C 3 CONIIC6H5 ~~SO2NH

CH2C~2CNH
(82) ~N=N~ OH C5Hll-t SHll-t S02NlI , ,, (83) . ~"
OH C5Hll-t CONE( CH2 )4-O~ C5Hll-t NHSO2--~ C~13.
2 ~3N=N~ 2 3 NH

Cl (84) OHC51l11~t ~CONH(CH2)4-0~ C5Hll-'~

Q NHCOCH2CH2~ ~H3 NH
~1 :' S57~
(85 ) C5Hll-t ' ~¢rCNH(CH2)4-o~ 5 11 CH2CH2--~} ~CH3 NH

~ NHCOCH3 (86) C5Hll-t CONH(CH2)4-0~ 5 11 t ~NHCOCH2CH2--~ ~ 2 5 HN

~Br (87) C~ 2)4- ~ c5~ t ( 88 ) C5~ t ~CONH(CH2)4-0~ C5Hll-t NHCOCH2CH2~ N=N--~ OCH3 HN

Cl ~.

( ~39 ) C5Hl l-t coNH(cH2)~-o~c5Hll-t ~;

~SO NH~ NH OC2H5 ~13r (90) ~N=N~OCi2 ~~2~ 5 11 ,", ~3 ONH(CH2)~,0--~C51~ t ~;

H
~N~N~ OH C5~-t Ph N ~ ~-~CONI~(C~2)4-~c5 (92) OH 5 ll t ~¢~CONH(CH2)4,-0~C5Hll_t NHS02~ CE~

2 ~ ~N~ OH C
H~ CoN~ ~ 5~ 11 ~_ N~\f ' :
~SO2~ ' ~.

- ~8- ~

;5 i79 (~3) :~
, N=N~ OH C5H~t 2 ~¢~ CONN(CN2)4-O--~ 5 (g4) C5Hll-t ,r~ Cl NHSO N=N~OCN3 ~.
HN

~Cl (95) C5Hll-t CONH ( CH2 ) 4-O ~ C5~ t CH
I`THCOCH2CX2--~N=N~ OC 3 NH
~,~

(96) C H
OH 5 ll-~¢~CONH(CH2~4-0--~C5X

NHCOCH2CX2~ N=N~ OCH3 HN

-69_ ~.

. .

(97) ~¢~ C 01111 ( cH2 ) ~l-O~ c5l~11-t NHCOCH2CI17 ~N=N~
HN
,, ~3 .:

(98) OI~ 5 11 ~CONH(CH2)4-0~C5 --I~3 SO 2NH
~3 N=N--~ OCH2(,0~H :

~ r 3 N=N~ CH3 (CH3)3C-C~12 C Cl- ~ 3 '; ~100) , -:
OH

n-H3 1C15~ S2 {~ C~2CH2~ N=N~ OHi :`
:

5S7~31 (101) OH
n 31cl$`~o~cH2cH2 e3 N=N ~OH
C1~C1 \ : :, OH

(102) HN
O~NHS02-~ CH2CH2~-N~OH ' lIN
" .

(103) n-H33C16-S02NH--~ 2 OCH3 NHCOCH2CH2~,~N=N~O~
IIN

(104) n-H33C16-0 ~ / C=N-NHS02 7 N~ICOCH2CT~2~
(CH2)3 N
S03H HN~

~.,~ ' ' 5S~ :

- (105) n-H29C~ NHCO-NlINH-So2~
NIICOCT,I2CH2 e~ N=N ~ OH
HN

~106) ~ ~, n-H31C15--;~ S02NHNHS02~ , NECOCH2CH2~ N=N~3 OH
HN

(107) ~N=N~ ~,~,CONH(CI~2)4-C~C5 ~ S02NH

~.',' .
(108) C5Hll-t ~,CONH(C 2)4-~ S 11 t ~N=
N~
IIN :

~Cl .' ,.

( 109 ) ' ' lC15--SO

(110) OH
¢ ~ CONHC1~3H~7 NHSo2-~9 ~<NHcocH2cH2_~
N=N~ OH , ~
HN .:
:' ¢~ , :
NHso2~9 :`
N=N--~ dl~ ~
.~ , HN .:
,~
(112 ) OH
. ~COM~I(CH2)4-0 ~S~ fC5~ t - ~ N=N~--OC~2CONH 5 11 557~
.

(113) ~ ~ C~5Hll t ~¢;;~co~ (c.l2)4-4~cs1~ll-t CH~ C113 ~502NH
~N=N-~OCH2CO H
HN , ~, ~ ':
~Cl :~

(11~) OH C5Hll-t ~¢ CONH(CH2)~~0~ 5 11 :

NHS02~
N~COCH2CH2~ ,' ' N=N~ QH
IIN

Cl ( 115 ) C5Hll-t NHCOCH20~ C5IIll-t ~LNHSO2--~ N=N~--OH ~ ~
O ~ ~.
~, ~SS~79 1 The compounds of the general formula ~I] or rII] used in the present invention are prepared accarding to the following process.
The above-mentioned Z-substituted amine subs-ti-tuted with two aromatic groups and a diazo compound ofan aromatic amine at least one of which aromatic groups and amine has a reactlve jointing group are subjected to a coupling reaction to prepare a shifted or non-shifted azo dye having a reactive jointing group. Alternatively, a diazo compound of the above-mentioned YC0-substituted amine substituted with two aromatic groups (in which at least either of the aromatic groups has a group of the formula -I~H2) and a diazo coupler at least one of ~hich aromatic groups and diazo coupler has a reactive jointing group may be subjected to the coup]ing reaction to prepare a shifted azo dye having a reactive jointing ; group.
Herein, the reactive jointing group means a group competent to participate in formation of the ~
X2 or X3 moiety in the above-mentioned general formulae.
~ hen, the M1 or M2 moiety is introduced into the azo dye having a reactive jointing group to obtain a shifted or non-shifted DRX compound. Further, if the (Ml or M2) - (gl, X2 or X3) moiety is introduced be-~ore-hand into such compound as to be a diazotized compoundand/or a diazo coupler, a shifted or non-shifted DRR
compound may be obtained directly simply by the coupling reaction as applied correspondingly to the above-mentioned reaction. Furthermore, by using a Z-substituted amine having or not having a reactive jointing group or the .

, .

lS~i7~?

1 above-mentioned (Ml or M2)-(Xl, X2 or X3) moiety instead of the above~mentioned amine substituted with two aromatic groups, the above-mentioned reac-tion is carried out and then at the suitable stage the reaction with a haloGen-substituted aromatic compound may be c~rried out tointroduce an aromatic group into amino group afterw~rd, thereby to obtain a shifted or non-shifted DRR compound.
In the above~mentioned reactions, when YCO is no-t introduced into an amine group o-f the above-mentioned aromatic group-substituted amine, the YaO group may be introduced into the amine group ~e.g. acylated) at the suitable stage of reaction to obtain a shifted DRR
compound. The shifted DRR compound may also be hydrolyzed to obtain a non-shifted DRR compoundO
~hen, the particular examples of the process for preparing the compound of the above-mentioned general formula ~I] or [II~ used in this inventionO
Synthetic Example 1 - Preparation of the exemplified compound (1) 5.0 g of ~-4-aminophenylpropionic acid was dissolved into 100 ml of water containing 20 ml of conc.
hydrochloric acid. Into the resulting solution, 10 ml of an aqueous solution containing 2.~ g of sodium ni-trite was poured at 0 - 5C~ After stirring for 20 minutes the reaction mixture was added with 0.2 g of sulfamic acid and then with 20.0 g of sodium ace~tate On the other hand, 5.7 g of ~-anilinophenol was added with 15 ml of trifluoroacetic acid and 15 ml of trifluoroacetic anhydride and the mixture was subjected ~0 to the reflux ~or one hourO Under a reduced pressure, 7~

1 excess of the trifluoroacetic acid and trifluoroacetic unhydride were distilled off and the residue was dissolved into 100 ml of ethanol. This solution was added with aqueous ammonia. While the resulting solution was kept at about pH 9, the above-mentioned diazonium salt solution was poured thereinto. After stirring for 30 minutes, the mixture was neutralized with an acetic acid and the resulting oily material was extracted by use of ethyl acetate. After washe~ with water, -the resulting solution was dried and the solvent was removed.
The residual oily material was purified by silica gel column chromatography to obtain 8.6 g of a pale yellow ma-terial having m.p. 161--165C, as shown in the following formula:
Compound (A) HOOCCH2CH2 ~ N=N ~ OH
~aoaF3 ' .

0.9 g of Compound (A) and 1.3 g of the compound of the following forrnulao Compound (B) ~;

OH C5Hll-t '^'~ -Co~E(~H2)~0--~ a,,Hll t l~HS02~

were dissolved into ~ ml of tetrahydrofuran. The r~sult-ing solution was added under ice cooling conditions S57~

1 with 1 ml of a tetrahydro~uran solution containing 004 g of dic~clohexylcarbodiimide and the mix-ture was stirred for four hours. Further, stirring was continued a-t a room -temperature for -four hours to prepare a white precipitate. ~he precipitate was collected c~nd the filtrate was concentrated and purified by silica gel chromatography Then reprecipitation was carried out in ethyleneglycolmonomethylether-water to obtain 0.74 ~ of a pale yellow material having m.p. 107-112C ~compound 10 (1)~
Synthetic ~xample 2 - Preparation of co~lpound (1) 0.9 g of the above-mentioned Compound (A) and 1.3 g of the above Compound (B) were added with 5 ml of a dimethylformamide solution containing N-ethoxycarbonyl-2-ethoxy-1,3-dihydroquinolineO ~.f-ter the admixture was stirred a-t a room temperature for 6 hours, it was cooled in an ice bath and -then added with 50 ml of an aqueous solution containing 1.5 g of sodium hydrogen carbonate.
The resulting precipitate was coLlected, washed with water and dried. The precipitate was purified by silica gel column chromatography. The resulting material was re-precipita-ted frorn ethyleneglycolmonomethylether-water to obtain 0.82 g of a pale yellow material having m,p.
104-110C [compound (1)].
Synthetic Example 3 - Preparation of compound (61) 2.0 g of the above-mentioned Compound (A) was dissolved into 60 ml of ethyl alcohol and the solution was added with 2 ml of 2N potassium hydroxide a~ueous solution. The mixture was stirred at a room temperature ~0 for 30 minutes and then neutralized with an acetic acid - 7~ -I.SSi79 1 and extracted with ethyl acetate. The extracted solution was was~ed with water, dried7 concen-trated and -then purified by silica gel column chromato~raphy. 1'he eluate is distilled to remove the solvent and then added with n-hexane to obtain 1.2 g of reddish brown crystals having m.p. 138-141C as shown in the folloT~Jing formulaO
Compound (C) HOOC~H2CH2 ~ N=N ~ OH

NH

0.7 g of Compound (C) and 1.3 g of Compound (B) were dissolved into 3 ml of tetrahydrofuran. The mixture was added under ice cooling conditions with 1 ml of a tetrahydrofuran solution containing 0.4 g of dicyclohexylcarbodiimide and stirred for four hours.
The stirring was continued at a room temperature for four hours. The white precipitate formed was collected and the filtrate was concentrated and purlfied by silica gel column chromatographyO ~urther~ the reprecipitation was carried out using ethyleneglycolmonomethylether-water to obtain 0.86 g of a yellow material having . .
m.p. 102~106C [compo~md (61)].
Synthetic Example 4 - Preparation of compound (61) 003 g of compound (1) was dissolved into 10 ml of ethyleneglycolmonomethylether. The solution was added with 0.5 ml of 2N KOH aqueous solution and stirred at a room tempera-ture for 10 minutes. The mixture was neutralized with an acetic acid and added with water.

5S~7~

1 The precipitate was filtered, washed with water, dried and then purified by silica gel column chromatography.
The re-precipitation was carried out using ethylene-glyco.Lmonomethylether water to obtain 0.2 g of a yellow materiaL having m.p. 103-107C [compound (61)~o Thus, -the various compounds of the above general. formula ~I] or [II] may be prepared in such manner as above. Among the said compounds thus prepared, the compounds were subjected to the measurement of ~n elementary analysis to show the results, as follows~

, 1~55791 0~ 0 N r~ ~ ~ 0 0 N
0 ~0 ~ 0 ~1 IS~ ~ ~ NCO :~ 1~ 0 0 ~J
~i C~ D r~ Dt~

h ~~1 ~ N 0 Ir~ OJ O ~ ~1 ~ ~1 ~ ~ O~ ~ O ~ O C~ ~ ~ 0 ~ LO Ll~ ~ ~O 15~ ~ ~O 15~

~e ~
_ 0 0 ~ ~ U~ ~ ~ ~~I Lr~ 0~ o ~q ~ U~ ~ o ~ ~ ~t ~ 0 ~~ U~
.~ ~ O C~ O ~ ~ O~O U~ C\~
P ~ ~o ~o ~o ~ O~ ~ ~ ~O ~O
3 ~

~ ~ ~ ~ O ~ O ~ O U~ ~ ~D 0 ~ ~ U~
a) ~ ~ ~ ~ ~ o ~ ~D ~ O
.

.

0 ~ O ~D L~ ~r~ I d t--~ N ~ 0 ~~
C~ ~D t~ Ir~ C) 1~ N1~ ~D ~ N
~ ~O ~

O ~ ~ ~ o` ~_1 N ~ ~

C~

l~S~9 N C~~0 t~i Lr~ 0 N. ~ O.~ . ~ ~ 1--0 ~o O
~I

U`~ 0 ~ 0 ~ 0 ~t<~t-- Lr\ 0 C~ ~-- ~ O U~ L
~ t\J C~~O cr, o~ ~ ~ o ~ G' ~ ~D 0 --1 ~t G~
Ls~ L~`\ Lr\ Ll~ L~ Lr~ U~ Ll~ ~O L~ Lr'\ Lt~ L~\ Lf~ ~O Lf~ Li'`

G~ ~O O~ J 0t-- L~ ~ 0 r l r-l N
Ll~ O ~ ~ ~1 ~ O CJ~~\1 1~ (~ G~ G' i~ 0 el 0 L~t~ L~ Ll~t~ cn N~1 Ir~ ~0 O N
O ~ ~ ~ O ~O ~O Lt~ O ~) ~ O ~O

L~ 0GL GL OL ~ ~ ~ O L~ ai~ ) N O ~D L~
G'a~ G~ O cr, 0 0 G' ~r-l Lf~ ~D 0 O1-- 01~ 0 ~D O

0 0 r-J ~~ Lr~ ~ N ~a~ N ~O --~ ~1 1~ ~I N O
~ ~ 03 Lr~CO00~D 0cr~ L;~ t ~ Lr\ L~ o ~ u~
Lr\ Lr~ L~ Lr~ Lr\ L~ L~ L~ Lr~ Lr~ Lr~ L~ Lt~ Lr~ ~7 L~ L~

o ~ o ~D ~ Lr~ ~1 ~ ~I L~ ~O ~ O
t-- N O ~\1 G~ d- N O ~ L~ 0 ~0 If~ Lr~
... .......... .
O ~ 0 Lr~ D Lr~ t ~ O N I--i LS'\ ~D O N
O ~ O ~ ~ O ~D ~O ~ ~D
`': ~.' ~O ~ 0 ~ O ~1 ~ ~r~ GL L~ 0 c;~ o ~1 ~1 ~Jrl N N N N N N N N N N

.

' ~

s~

N 0 ~ O Ll~ l i~ O O ~ d'0~ --1 r~ D ~ r-l O ~0( ~ 0 N ~ ~ ~0 11~ 1-- r~
1~ ~o1~ C~ 0~ot~ 0 0 --l 0r-l ~ ~ ~11~ ~ --1 0 r-l r-l ~\ N r~ 0 r l (U ~ a:~ ~D.0 03 ~1 0 l-- O ~

':

~ ~I r~ ~ 0 ~ ~ 0 0 ~ r~ ~ O~ O U~
0 ~0a~ ~ ~'tCO 1~ ~-1 N Or~ 0 .
~O L~ O ~ ~O ~ ~~O ~ ~O ~O ~O~O ~ ~

~ r-l N 0~ r-l \D Lf~Li~r~l O d- r- ~~1 ~ (~ N
a~ a) 0 ~-~ o ~ 0 ~ ;t ~ N ~ t-- t-- ~ ;~

Lt`\ ~ N 1~ ~ ~ O ~ L~ NO
O~OLt~ O ~O~O Lt~ ~O ~O

r-l O 0`~ r-l ~ O ~t ~ t~ N r-l ~ N r-l 0 ~0 C--~0 ~ ~ N OC-- C~ 0 ~ l O N
~O 1~ O ~O ~O~O~O ~O ~O ~O ~O ~D ~O ~O ~O ~ ~O

~\ ~\t `\ ;~ ~\ ~ ~ G~ ~t ~t 't ~t ~t ~t ~t G'' ;;t ~ 83 -~ ~5i5'7~

0~ ~ 0 ~ ~~ u~ u~ c~ ~ ~ r~ . .
~i 0 ~ ~ ~ ~ ~~ 0 0 0 ~ ~ ~ 0 . .

~ N 0 N~ 1 ~1 ~I NN ~ Lf\ a~` O~
N N ~ U~ C5~ NLl~ G' C~ ~ D ~ C-- ~--O O ~' -- 0 01'~t~\N 0`.L~ O N ~ ~ ~) `.
N ~ ~1 1~ 0 r-N~57 N C-- N N U~~1 ~ . . . . . . . .
O ~ '~ ~ O ~ N N C~) ~

; ' - .:
: .
N O C~ O O--1 G- O ~1 ~IN O O O O ~ 1--l tD N~ OL'~ ~ G' L~ a~Lr~ N G' ~ ~D N
,~ co r- r- r- c~ ~ ~ r- r- ~ 0 0 ~ r- t~ co Ci`\ ~ I--l N ~ G' a~ r- o~ 0 r-- N C)~ --1 ~I N O
N O L" ~O ~ G~ N G' ~ L'~ '~t L" N r-- r-- N N
.~ ........ . , , ~O ~O Ll`\L'~ D L'~L'~ 11~ L'~ Lr~

N ~0 ~ O 0 N~~0 N r- Lr~ L~ O Ll~
O G' ~)t ~O ~ ~0 0~) t~ 0 d- r- ~ ~ ~ o ~i L~ D 0 ~~--~ ~ O ~) N N 0 0 ~) ~O~O~S:)L'~ O ~ r-' :

O ~I N t<~ G' L~ ~D ~ 0; ) Ci~ O r-l N ~ d' L~
li~ L~ L~ 15`\ Ll~ L~ L~ L~ L'~ L'~

~5~

0 Ll~ O Ir~ r-l CO ~ 0 U~ 0 0 ~-1 N O Ci~
1~ Ll~ CO 0 0 Lr~ ~5) ~ O ~0 N t ~
0 ~~ ~ 0 ~ ~ 0 0 ~ --I :

0 NC~~ ~ ~I_ N 0 0C~ ~ O 0 0 t<~ N 0 0 N1~ 0 0 ~N ~Lr~O Or~

t-- ~ O O O NLt~ O ~CJ~ r-l 01--lr-l ~ 1~ ~1 o ~ ~~ ~ ~1 ~a) o o r--u~o ~u~ ~ oc~
~ ~D ~ ~~D ~ ~~O ~~ ~~ ~ t~ O ~O

0 11~C-- Nt~C-- O 1~ lr~ 0 0~ii 0 ~ CO 1~ t<~
~ 0~a~ 01~(~ ~-1~1 0Lt~ ~0 ~c-- 0 0 ~~ ~ ~ ~ ~ 0 0 ~0 0,,~0 0 ~ N~O~ 0 0tS~ J O0 ~
. ~ . . . ~ . .. . . . .

DU~~1 ~ t~ 0 NN ~D ~ OL(~ O C~) N1~ 0 0(~ ~ ~ N CO~D 0 O C~ O ~L~ or- ~D 0 0tS~
O ~ O~O ~ D1~ O~O
.

~ 0(~O~I Nt~ 0~ 0C~ O ~ N
.

- ~5 -S~

Lr~ N N N O Lt~ , N C~i ~ILr~ r--i O ~ a~ 0 O N 15~ 0 0 N t ~ ~D ~t 0 tl~ O ~ 0 ~t O
co a~ 1~ r 1 1~t'--0 ~\ L-- C~) t-- 0 a) 0 0 0 L~

`,, O L~ C-- 0 1~ ~ N OLr~ a~ ~ ~ 0NN L t~
~O ~O ~O L~ ~O Ll'\ ~O Ll~ U) L~ L5~ ~O ~O ~O ~D ~O ~O

N Ll~ Lr~ t~ ~ L~ C~ Lr~ N O ~O O L~ L~ a~ ,~ o ~I N ~ 1~ N 0 CS~ N C)`\ l-- Ll~ O 0~ ~) ~. O C~
~) Lr~ ~x) a~a~ 0 ~; Lr~ ~ r i O r~ N
1~ ~D ~ ~O ~ O ~O ~O ~ ~ C~

0 ~1 ~ ) 0 0 ~ ~t Lr~ ~Ot ~ O ~ (~' N ~ r~ Lr~ C~Lr~ r-l ~t~I N r~ O r-/
C~: ~ ~ ~ L-- t-- C:) C~ L-- C~ 1-- 0 0 ~ 0 O~

L~ ~ N a~ 0 t~ ~I t~--t Gt O N r-- ~D
Gt ~0 N O G'' ~ ~a~Gt t-- Lr~ G' L~
~o ~ ~0 ~0 ~0 L5~~0 LS~ ~0LS~ 3 ~ 0 ~1 ~t N N a~ O 't --t ~DGL ~ IS~ N LS~ ~t -- 0 Lt~ ~ ~t 0 ) . C-- 0 0 ~ Gt C~ O ~L) Lr~ 0 O 0(X~GL L~ i O I--i O N Ci~
O ~O ~O ~D ~O ~D ~O 1 GL Ln ~ 0 ~ O r--~N 1~\ GLL~ ~:) 1~ 0 ~ ~
0 a) 0 0 ) 0 c~ ~ O

_ ~36 -.

iS7~

t-- ~ cr 0 0 ~ ~-~ ~ o o t-- o ~ ~ 0 o o ~ 0 t ~ a~0 ~~ ~0c-- 00 ~1 0 ~ 0 0 ~O ~IS~ ~ O ~U~ r~ ~ N O~
t~ I~ 0~~It-- O~1 O C~ r-l r J ;-~ r-)/
~O ~ O1--~O~O ~O [`-~O 1~ ~O ~) ~O ~O

Cj~r-lr-~O1~~ O ~ O t~
U~ ~t Ot~J~015~ ~ 0 N . 1~ ~ t~
.. ..
O r-l~t~L~L~ ~ ~~ 0 0 r-- 0 0 0 o~D~O~D~O ~O r- ~o ~D ~O ~O ~D ,, OOt~~ 0 ~ O r ~ ~
(~J ~0~ 0~ 0~0~ -! 1~ r~ l 0 u~ O~ X a~ ~ ~ ~ ~ c~ co .~ 0 a) 0 0 ~D 0~O 0 O ~D O ~t t~l 0~ I0~ r-l O
0~ .D ~ 0rl ~ Or~ 1 O ~
.
~O ~ O ~ ~O ~ ~O ~ ~ ~ O ~D

~ ~J r-(rJ~t ~O ~ t~i~ ~ ~1O~ U`\ O~
CO r-l r-~ OIr~~t ~ :;.' O~ 0 C ) ~ O L
O r~ ~ ~ Ll~ IS~ O~ 1-- ~ O 0 t-- 0 0 C~) 1~~O ~ O ~O ~O

O O OO O O OO O r-l r-~ r~ r-l r-l ~1 r-~ r-l r-~r~r-lr-l~I r-l r-l r-l r~ r-l ~I r-~ r l ` ~ ` . .. .

~557~

The present invention will be explained in further :.
detail.
The photographic element of this invention comprises at least a photosensitive element containing a silver halide emulsion layer and a compound of the above-mentioned general formula [I] or [II] as a DRR compound.
More particularly, the invention relates to a color diffusion transfer photographic element which comprises a silver halide emulsion layer and a yellow dye image-forming compound represented by the formula:
R(l) R(2) [Ml~(Xl)q ~ Al'-N=N ~ R(3) ` :

R ~ (R ))w wherein Al' represents an aromatic hydrocarbon group or an aromatic heterocyclic group R(1), R( ) and R(5) each repre-sent hydrogen, halogen, nitro, an alkyl group, hydroxyl, alkoxy and aryloxy, a group of the formula -OCOY~ (herein, the O- in the -OCOY' group represents a hydrolyzable group); R(3) is as defined with respect to R( ), R( ) and R( ), or the group Z' ; -N-A3 [ (X2 ~ Ml]n' and R(4) represents the group Z' -N-A3 ~ X2 ~ Ml]n' in which A3 is an aromatic hydrocarbon group or an aromatic heterocyclic group; X2 is a divalent joint group; Z' is hydrogen or the group YC0- (the YC0- is a hydrolyzable group);
Ml is a monovalent dye releasable group Xl is a divalent joint group; q is 0 or 1; m is 0 or a positive integer, n is an integer not less than l; r is 0 or 1; and w is an integer from 1 to 4.
~ - 88 -'7g The silver halide emulsion is a hydrophilic colloidal dispersion of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, or the mixture of these silver halides. The emulsion may include, in addition to conventional emulsions, those which are prepared in various processes, such as the so-called conversion emulsions, Lippmann emulsions and direct positive emulsions like ones fogged beforehand or of the internal latent image type~ And, the grain size, content, a mixture ratio or the like of silver halide differs according to the kind of a photographic element.
As a hydrophilic protective colloid which is a binder for silver halide, there may be used various natural or synthetic materials such as gelatin, gelatin derivatives or polyvinvyalcohol, etc., singly or in combination.
The silver halide may chemically be sensitized by using active gelatin, a sulfur sensitizing agent such as allylthiocarbamide, thiourea, cystine, etc.' a selenium sensitizing agent, and/or a noble metal sensitizing agent such as gold, ruthenium, rhodium, iridium, etc~' singly or in suitable combination. Further~ the silver halide emulsion may also be sensitized optically, for example,

- 8~a -~g 1 by using cyanine dyes or merocyanine dyes. Gener~lly a light sensitive silver halide color photosensitive element may be p,epared by using three kinds of silver halide emulsions whieh respectively have light sensitivi-ties different in wavslength region.
'~he silver halide emulsion may be stabilized by triazoles, tetrazoles, imidazoles, azaindenes, quaternary benzothiazolium compounds, zine compounds or cadmium compounds and may eontain a sensitizing eompound of e.g.
quaternary ammonium salt type or polyethyleneglyeol type.
The emulsion may eontain a sultable gelatin plasticizer sueh as glycerol, dihydroxyalkane like 19 5-pentanediole, ethylenebisglycolic acid ester, bis-ethoxydiethylene-glyeolsuccina-te, polyacrylic amide latex and, further9 eontain a gelatin hardening agent such as formaldehyde, a halogen-substituted fatty acid like mucobromic acid, a compound having an anhydride group, dicarboxylie chloride, a methanesulfonic acid biester or a so~lium disulfite derivative of dialdehyde wherein the aldehyde groups are separa-ted by 2 or 3 carbon atoms; a coating aid sueh as saponin, and sulfosueeinate 7 or other various photographie additives. Moreover, if desired, the emulsion may contain various other additives ordinally used in conventional photography such as an antifoggant or an ultraviolet absorber.
In this invention, various kinds of silver halide emulsions may be used as mentioned above. In ease using a nega-tive silver halide emulsion, a negative color diffusion transfer image may be obtained. A
positive color diffusion transfer image can be obtained _ ~9 _ ~15~i7~

1 in various processes.
~ or example, the processes include such process using a direct positive silver halide emulsion as disclosed in U.S. Patents 3,227,552, 2,592,250, 2,0057~37, 3,3S7 ? 778 and 3,761,276, Brltish Pa-tent 1,011,062, Japanese Patent Publication No. 17,184/66 and Japanese Laid-Open-to-Public Patent Publication ~o. 8,52~/75, such process using physical developmen-t ~s disclosed in British Patent 904,364 and Japanese ~aid-Open-to~Public Patent Publication No. 325/72, and such process using a negative silver halide emulsion layer con-talning a compound releasing a developmen-t inhibi-tor by reacting with an oxidation product o-E a developing agent while a fogged emulsion layer adjacent to the negative emulsion layer is added with a color image ~orming ma-terial, as disclosed ln Japanese Patent Publication No. 21,778/68 and U.S. Patents 3,227,554 and 3,632~345.
A positive color dif~usion transfer image may be prepared in various processes as described above.
Preferred is a process using a direct positive silver halide emulsionO One example of the direct positive silver halide emulsion, is a silver halide emulsion which is developable b~ subjecting beforehand to exposure over its whole surface or chemical process but becomes to be imagewise non-developable by imagewise exposure.
Another example of the direct positive silver halide emulsion is a direct positive silver halide emulsion having light sensitivity mainly inside silver halide grainsO In this invention, the latter direct positive silver halide emulsion is pre~erable. In this -- ~0 --S7~

1 direct positive silver halide emulsion9 latent images may be formed mainly inside the silver halide grains by imagewise exposure and the surface development under fogging conditions causes the formation of positive 5 silver images.
There are various processes for such development under the fogging conditions. ~or example, there may be used the so called air fogging developer as disclosed in W. German Patent 850,383 and U,S. patenJG 2,497,875, or the flash exposure over the whole surface at the time o~
development The latter process are disclosed in W. German Patent 854,888, U.S. Patent 29592,298 and British Patents 1,150,553, 1,195,838 and 1,187,0290 Further, it is possible to carry out development in 15 the presence of a fogging agent. As a fogging agent used for such case 9 there rnay be used hydrazine type compounds and N-substituted ~uaternary ammonium salts singly or in combination. These fogging agents are disclosed in U.S. Patents 2,58~,982, 3,227,552, 3,61596159 3971~,494, 20 3,734,738 and 3,718,470. Although the amount of a fogging agen-t may be selected within a wide range -depending on the use purpose, it is generally 0.1-2~0 g based on one liter of a developing solution in case of adding into the developing solution and 0.01-0. 2 g/m2 in 25 case of adding into a photosensitive element~
In this invention, the photosensitive element comprises a combination of the above-mentioned silver halide emulsion and the compound of the above general ~ormula ~I~ or ~ as a DRR compoundO ~y using one or 30 two of such combinations of sllver halide emulsions and S~'7~

1 DRR compounds, there may be obtained a unicolor dye image or a l~icolor dye image, for example, ~or quasi-color photograph. And, in case of usin~ for a color diffusion trans-~er process, for example, according to a multi-color substraction process, blue light sensitive, green light sensitive and red light sensitive silver halide emulsions are combined as associated with yellow, magenta and cyan DRR compounds respectively.
A preferable multi-layered construction comprises successively the blue light sensitive emulsion layer, the green light sensitive emulsion layer and the red light sensitive emulsion layer from the exposure side. In this case, a yellow filter layer may be placed between the blue light sensitive emulsion and the green light sensitive emulsion. As an example of process for combining the light sensitive silver halide emulsion and the DRR compound, there may be a process adding them separately into the layers adjacent to each other. ~ut, in case of using such short wavelength shi~t type D~R
compound as having the group of the ~ormula YC0 as Z in the general form~a ~I~ or ~ , it is possible to add said DRR compound into the silver halide emulsion bscause the DRR compound does not reduce the sensitivity of the emulsion.
Further, there may be such mixing packet process where not less than two combinations of the silver halide emulsions and the DRR compounds are presented in one layer, as disclosed in U.S. Patents 2,800,458 and 3,466 9 662.
The DRl~ compound used in this invention is ~5~17~

1 dissolved in as small an amount of organic solvent as possible and dispersed into a hydrophilic protective colloid, such as gelatin or polyvinylalcohol, wh;ich is a binder of the silver halide emulsion layer or its adjacent layer in the photosensitive element. As the organic solvent, there may be used a high boiling;solvent, a low boiling solvent which may be removed away by evaporation, or an organic solvent easily soluble in water, singly or in combination.
As a particularly useful high boiling solvent in this invention, there may be included ~-n-butyl-acetanilide, diethyllaurylamide, dibutyleaurylamide, dibutylphthalate and tricresylphosphate. As a useful low boiling solvent, there may be included ethyl acetate, methyl acetate and cyclohexanone. These low boi]ing solvents can be removed by evaporation at the time of drying after coatin~ to form a layer or may be removed before coating in the manner as disclosed in U.S. Patent 2,801,171.
As an organic solvent easily soluble in w~ter, there may be used 2-methoxyethanol and dimethylformamide.
Instead of or in addition to the high boiling solvent, various lipophilic polymers may be used. As the lipophilic polymer, there may be used polyvinyl acetates, polyacrylic esters and polyester of polyhydric alcohol and polybasic acid.
In this invention, useful for dispersing the DRR compound of this invention is such process as disclosed in Japanese Patent Publication Nos. 13,837/68 and 32,131/73, U.S. Patent 3,832,173 and Japanese ~aid-SS'7~

1 Open-to-Public Patent Publication No, 17,637/75, Among the compounds of the above-mentioned general formula ~I] or ~II], the D~R compounds having a water soluble group such as a carboxylic group or a sul-~o group may be dissolved into water or an aqueous alkaline solution and then dispersed into a hydro~hilic protective colloid and, if necessary, it may be neutralized.
~ he amount of the DRR compound used in this invention may be selected within a wide range according to the kind of compounds to be used and desired results.
For example, it is preferable to use about 0.5~0 to about 10~ by weight of the compound in the water soluble organic colloid coating solution as used.
In case of carrying out a multi-color diffusion 15 transfer process, it is advantageous to use inter layers in a photographic element. The inter layer comprises gelatin, polyacrylamide, calcium alginate, partial hydroly~ate o~ polyvinyl acetate, a hydrophilic polymer -~
like hydroxypropylcellulose, or such polymer, formed from 20 a latex of a hydrophilic polymer and a hydrophobious - polymer, as disclosed in U.S. Patent 39625J685.
~urthert usable for the inter layer may be such compounds as disclosed in UOS Patents 3,384,483, - .
3,421,892, 3,427,158, 3,121,011, 3,0439692~ 3,059,263j 25 3,615,422, 3,625,685, 3,756,816 and 3,069,2640 In order to avoid color mixing or color contamination due to diffusion of an oxidation product of a developing agent into other layers9 it is preferable to add, into the inter layer or a layer between a silver 30 halide emulsion layer and an image receiving layer in a ~557~

1 photographic elemen-t, a coupler, such amidra~one ompound as disclosed in Japanese ~aid-Open-to-Public Patent Publica-tion No. 15,532/73, such hydrazone compound as disclosed in W. German Pa-ten-t 2,123,2689 or a non-di-ffusible hydroquinone derivative. The non-diffusible hydroquinone derivative may further be added into a silver halide e~ulsion layerO
As a support for a photosensitive element of this invention, there may be used various natural or synthe-tic polymers such as paper, glass9 cellulose nitrate, cellulose acetate, polyvinylacetal, polycarbonate, polystyrene, polyethylene terephthalate, polyprop~lene and polyethylene. These may be transparent or opaque depending on the use purpose.
~urther, a vapor permeable support or an oxygen ;~
barrier support as disclosed in U ~. Patent 3,573,04~
may be used advantageously. Moveover~ in case of using a transparent support, it is preferable tha-t the support is colored to such an extent as not to prevent an exposure and visual observation of formed images but to avoid fogging of an emulsion layer at the -time of processing due to piping light coming in -from the sides of the support.
In this invention, the above~mentioned photo-graphic element was exposed imagewise and then the photo~sensitive element was developed in the presence of the below-mentioned silver halide developing agent combined with the below-mentioned alL~aline processing solution.
By this development, the compound of the above general ~0 formula ~I~ or ~ and other D~R compounds placed in the - g5 -~:1557~

1 photosensitive element release diffusible dyes imagewise.
These diffusible dyes are diffusion-trans~erred to an image receiving layer which is placed in a superposed relation with the above-men~tioned photosensit,ive element at least during the development and then dyed in the image receiving layer, to prepare color images I-t is preferable for the image receiving layer to contain a mordant. ~;
As -the mordant suitable to the image receiving layer, there may be used any of those which have a preferable mordanting effect on the diffusible dyes or their precursors on way of their diffusion transfer~
Useful are such as poly-4-vinylpyridine9 poly-4-vinyl-N~
benzylpyridinium-p-toluenesulphonate and cetyl -trime-thyl ammonium bromide~ The mordant which may be advantageously used in this invention includes such as disclosed in U.S. Patent 29882,156, Belgian Patent 729,202, UOS~
Patents 3,488,706, 3,859,096, 3,788,855, 3~227,1~
~,271,147, 3,709,690, 3,625,69~, 3,770,439 and 3,7569814, and Japanese ~aid-open-to~public Paten-t Publication No. 61,228/75.
The above-mentioned mordant is generally used in various binders such as gelatin, polyvinylalcohol9 polyvinylpyrrolidone or wholly or partially hydrolyzed celluloseesterO Solely such binders having a mordan-ting e-~fect as poly-N-methyl-2-vinylpyridine9 ~T-methoxymethyl-poly hexylmethyleneadipamide, a copolymer or polymeric mixture of vinylalcohol and N-vinylpyrrolidone, partially hydrolyzed polyvinylacetate, acetylcellulose, gelatin9 polyvinylalcohol or a guanylhydrazone derivative of 1L 5 ~

1 acylstyrene polymer may be used for an image receiving layer as far as the mordant is concerned.
As a special example 9 the mordant may be contained in the alkaline processing solution as 5 disclosed in Japanese ~aid-open-to-public Patent Publica-tion No 47~ 626/750 The image receiving layer may also contain an ultraviolet absorbing agent, a fluorescent whitening agent or various o-ther additives ordinarlly used for convelltional photography.
After forma-tion of dye images is substantially accomplished following a diffusion transfer of diffusible dyes due to application of an alXaline processing solution, it is necessary to reduce a pH within a pho-to-15 graphic element to about neutrality, so that thestability of the dye images is augmented and additional image formation is substantially stopped to inhibit discoloration or contamination of the images as caused at a high pH. Therefore, it is advantageous -to use a 20 neutralizing layer containing such material as reducing the pH sufficiently. As the material, for example, such ~ r polymeric acid, its partial ester or anhydride as disclosed in U.S. Patent 3~ 362 ~ 819~ such higher fatty acid as disclosed in UOS. Paten-t 2~983~606 and such 25 metallic salt of solid acid as disclosed in U.S. Patent 2 ~ 584 ~ 030 are useful in this invention.
Further, microcapsulation as disclosed in U S~
Patent 3~576~625 may be carried out.
It is preferable, moreover, to use a timing layer in order to control a reducing speed of the p~Io - 97 ~

iS~

1 As the material for said layer, there may be used, ~or example, gelatin, hydroxypropylcellulose~ partially hydrolyzed vinyl acetate-acryl latex, polyacrylamide, acetylcellulose, polyvinylalcohol, partlally acetalized 5 polyvinylalcohol and the mixture o~ these~ This timing ;
layer is usually employed in combination with a neutralizing layer. ~he combination may be placed on a support of a photosensitive or image-receiving element or a support of cover sheet which sheet will be explained later. Ordinarily, the timing layer is positioned between the neutralizing layer and a space in which an alkaline solution is spread.
~ he alkaline processing solution used in -this invention contains a component necessary to develop the silver halide emulsion and form the di~ usible dyes and has a high alkalinity, generally at more than pH 10.
The alkaline processing solution used in this invention contains an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide, potassium hydroxide, calcium hydroxide and lithium hvdroxide, or sodium carbonate or diethylamine It is pre~erable, moreover, that the alkaline processing solution contains a silver halide developing agent.
As the silver halide developing agent used in this invention, there may be included, ~or example, hydroquinone, l-phenyl-3 pyrazolidone~ 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, aminophenol, N-methylaminophenol~ N,N-die-thyl-p-phenylenediamine, ~S~

1 3-meth~ T,~-diethyl~p-phenylenediamine and 3-methoxy-~-e-thyl-N-ethoxy-p-phenylenediamine.
Although various silver halide developing agents may be used as mentioned above, a black-and-white silver halide developing agent i 3 particularly preferred to reduce possible co-ntamination at areas where the dye images are formed. Although the above-mentioned silver halide developing agent is generally contained in the alkaline processing solution, it may also be contained beforehand in a photographic element. Further, it may be also contained both in the alkaline processing solution and in the pho-tographic element. In case of containing said agent beforeb~and in the photographic elemen-t, it may be contained in the form of its precursor.
It is also preferable that the alkaline solution is added with such compound as hydroxye-thylcellulose or carboxymethylcellulose sodium salt. `
~ ur-thermore, the alkaline processing solution ~ay be added with such compound (suitab~e to improve ; 20 photographic properties) as a sodium sulfite, potassium bromide, a triazole type compound or a mercapto type compound.
Although the above-mentioned alkaline processing solution may be applied in various ways to the pho-to-sensitive element, it is preferable that -the solution is held in a rupturable container and is applied to the exposed photosensitive element af-ter exposure by rupturing said container by means of pressing materials equipped in a camera and/or a cartridge for a photographic element~
~0 As a rupturable container, such container as _ 99 _ :

~55'7~

1 disclosed in U.S. Patents 2,543,181, 2,643,886, 2,72~ 9 051, 3,056,492 and ~,152,515 may be used~
In addition to -the above-mentioned photo-sensitive element, the photographic element in this invention may comprise an image receiving element and a rupturable container, while the photosensitive element and an image receiving layer of the image receiving element may be placed as separate before exposure or both may be combined as one body to form a unit. After the processing, the photosensitive element and the image receiving element may be combined as one body or the photosensitive element and the image receiving element may be stripped off from each other~
In the case that the film unit was used in such process as placing the photosensitive element and the image receiving element detachedly before the exposure or as stripping away the photosensitive element and -the image receiving element from each other, it is required to form the image receiving layer on another support which is not common to that of the photosensitive element.
As the support for the image receiving layer in the image receiving element, the same material as for the support of the photosensitive element may be used and it may be transparent or opaque.
The image receiving layer may also be formed on the support of the photosensitive element and in this case it is preferable ordinarily to use the so-called cover sheet, in order to spread the alkaline processing solution between the cover sheet and the photographic ~0 element. As the support of the cover sheet, there may , 57g 1 also be used the same as the photosensitive element.
It is good to form, as a background for formed images, a light reflecting layer having a high white~
ness. Although the position o~ the light reflecting layer is not par-ticularly restricted, it is good to form the light reflecting layer between the photosensitive element and the image receiving element ln the case that the photosensitive element and the image receiving element are not stripped off from each other after processing. The light reflecting layer may be formed beforehand as a layer or such layer may be formed between the photosensitive element and the image receiving element at the time of processing by providing a light reflec-ting agent in the alkaline processing solution.
As -the light reflecting agent, there may be used titanium dioxide, zinc oxide, barium sulfate9 flake silver, alumina, barium stearate or ~irconium oxide, singly or in mixture of two or more kinds. In case of forming beforehand the layer, the said agent may be dispersed into an alkaline solution-compatible binder, such as gelatin, polyvinylalcohol or any other suitable binder.
As a process for forming the light reflecting layer9 for example, such process as disclosed in Japanese ~aid-open-to-public Patent Publication ~os. 486/71 and 477/72 may be used.
The above-mentioned light reflecting layer may also be added with a whitening agent such as stilbene or coumarin~ In case of developing the silver halide emulsion under room light after exposure9 it is preferable to provide an opacifying layer in order to protect the ... . ~.
: :

557~

1 silver halide emulsion from undesired light exposure.
The opacifying layer may be formed beforehand as a layer or formed at the time of processing. As the opaci-fying agent, there may be u7ed carbon black or such indicator dye as disclosed in Japanese ~aid-open-to-pub]ic Patent Publication Nos. 26/72, 27/72 and 28~72. It is also advantageous to use such desensitizer as disclosed in U S Patent 3,579,333.
The light reflecting layer and -the opacifying agent layer, bo-th as mentioned above, may be presented as the same layer or as separate layers adjacent to each other.
Although various layer arrangements as the photographic element may be used, such element as dis-closed in U S. Patents 3,415,644, 3,4159645~ 3~415,646,3,473,925, 3,57~,042, ~,57~,043, 3,59~J164, 3,594,165~
3,615,421, 3,576,626, 3,658,524l 3,635,707, 3,672,890, 3,730,718, 3,701,656 and 3,689,262, Japanese Laid-open-to-public Patent Publication ~o. 6,337/75 and Belgian Patents 757,959 and 7579960, may be used in this invention.
In the above-mentioned various film units~ if desired, a -filter dye suitable to improve photographic properties may be added at any position of the exposure 25 side of the silver halide emulsion. As the filter dye, those which are stable at an ordinary pH but become colorless due to decomposition or the like~ when they contact with the alkaline processing solution may be used.
A-fter the diffusion transfer of dye images to 3Q the image receiving layer is carried out9 there remain S~

1 the images of silver images and dyes or dye precursors in the photosensitive element as a func~ion of the diffusion transferred images. If this ~ilver or residual silver h~lide is removed by processing in a bleaching bath and then in a fixing bath or in a bleaching-fixing bath while the dye precursor is transferred to a dye, there may also be the dye images reversed from the dye images formed on the image receiving layer.
x ~ le_l Photosensitive element (I) was prepared by successively forming the following layers on a transparent polyethyleneterephthalate film support having the thick-ness of 110 ~m:
(1) A layer having the dry thickness of 1.1 ~m, contain-ing a blue-light sensitive silver iodobromide emulsion in a silver amount of 11.3 mg/100 cm2 and a gelatin amount of 122 mg/100 cm2, (2) A layer having the dry -thickness of 1.5 ~m, contain~
ing compound (1) in an amount o-f 8.0 mg/100 cm2, tricresyl phosphate in an amount of 4~0 mg/100 cm2 ~nd gelatin in an amount of 14.0 mg/100 cm2, and (3) A protective layer having the dry -thickness of OO9~m, containing 10.0 mg/100 cm2 of unhardened gelatin~
Then~ photographic elements (II), (III), (IV), (V) and (VI) were prepared by carrying ou-t the same procedures in the case of photographic elemen-t (I), except that, instead of compound (1) used in preparation of the said element (I) 9 compolmds (6) 9 (9), (61), (66) and (69) were respectively used.
Those layers of the photosensitive elements LSS7~

1 which contain the compounds o~` the invention were prepared in the following manner; at first, dissolving the compounds individually into e-thyl acetate an~
tricresyl phosphate, dispersing the resulting solution in an aqueous gelatin solution containing ~lkanol~
(Du Pont de Nemours & Co.) as a surfactant and then coating the dispersion.
Next, image receiving elements were prepared by successively forming the following layers on a cellulose acetate-coated baryta paper supportO
(1) A neutralizing layer having the dry thickness of 25.0 ~m, containing 24.8 mg/100 cm2 of polyacrylic acid, (2) A timing layer having the dry thickness of 3.0 ~m, containing 5.0 mg/100 cm2 o-f cellulose acetate, and (3) An image receiving layer having the dry thickness of about 20 ~m, containing 22.0 mO/100 cm2 of a copolymer of styrene and ~T-benzyl-~T/N-dimethyl-N-(3-maleimidepropyl) a~noniurn chloride at the ratio of 1019 and 22.0 mg/100 cm2 of gelatin.
Photosensitive elements (I) to (VI) were exposed from the support side through a 30-step silver wedge with each density difference of 0.15. Then, the exposed photosensitive elements were superposed on the above-mentioned image receiving element while 1 0 ml of the ~ollowing alkaline processing solution was spread there-between, thereby to carry out the processing~
Alkaline Processing Solution Potasslum hydroxide 28.0 g Sodium sulfite 1.0 g 1-Phenyl-3-pyrazolidone 4.0 g ;
:' ~5~

l 5-Methylbenzotriazole 1.4 g Carbon black (MA-100 by Mitsubishi Chemical Industries, Ltd.) lOO.O g Sodium carboxy methylcellulose 50.0 g Benzyl alcohol 5.0 ml Distilled water -to make total1000 0 ml .

After two minutes, the image receiving elements were stripped off from the photosensitive elements and dried.
The reflection density of the trans~er images thus obtained was measured by use of a blue filter to determine their maximum densities (Dmax) and minimum densities (Dmin) as followso Photographic _Element _ max. _~min.
(I) l.90 0.22 (II) 1087 0.21 (III) 1.97 0 23 (IV) 1093 0.22 ~V) 2.01 0.23 (VI) 1.86 0.20 On the other hand, then, photosensitive elements (I) to ~VI) were exposed in the same manner as above except but from the opposite side of the support. ~fter two minutes~
the image receiving elements were stripped off frQm the -~
photosensitive elements and dried~ The reflecting density of the transfer images thus ob-tained was measured by use of a blue filter. The data obtained were compared with those in the cases of the exposure from the support side to show a reduction ratio in sensitivity, as followso 1 Photographic Element ,`.-~ lo~ E
(I) 0.06 (II) 0,05 (III~ o.og (IV) 2.30 (V) 2.~3 (VI) 2.47 :

From the above result, it w~s understood that photosensitive elements (I), (II) and (III) using respectively compounds (1), (6) and (9)9 which are the shift type DRR compounds, showed a remarkably small decrease in sensitivity in comparison with photographic elements (IV), (V) and (VI) using such non-shift type DRR compounds as compounds (61), (66) and (G9).
The similar result was also o~tained by using, in the case of forming the layers of above photosensiti~e elements (I) to (VI) containing the compounds, the ' following procedures The compounds were di.ssolved into ~':
acetone; the resulting solutions were filtered to remove those insoluble in acetone9 the resulting filtrates were poured into water to deposit the above-mentioned compounds9 the deposits were collected by filtration9 the masses thus obtained were washed with wa-ter9 7 wt/% ;~
of the exemplified compounds were added to water containing 0.7 wto~ of Alkanol-XC to prepare aqueous slurries9 the slurries were dispersed by means of a supersonic homogenizer into an aqueous gelatin solutions, - and, the coating thereof was carried out, ,.~

- 106 ~

5st;~9 1 Exam~le 2 ._ A multi-layered multicolor photosensitive element ~as prepared by successively forming -the following la~ers on one side of a ;oolyethylene terephthalate film support having the thickness of llO/~m, on the other side of which was coated with a layer of 25 mg/100 cm2 of carbon black and 45.0 mg/100 cm2 of gelatino (1) A layer having the dry thickness of 1.5 ~m, contain-ing 13.2 mg/100 cm2 of a cyan DRR compound having the following formulao OH C5Hll-t CONH (CH2 ) 40--~ C5~ 't 2~ ';
~ ~02NH

02N~N=N~
2 ~ :
and 17.0 mg/100 cm2 of gelatin, (2) A layer having the dry -thickness of 1.4 ~m, contain-ing 1403 mg/100 cm2 (as silver amount) of a red light-sensitive, internal latent image type silver iodobromide emulsio.n, 0.7 mg/l.OO cm2 of potassium 2-octadecylhydro-quinone-5-sulfonate, 0.14 mg/100 cm2 of form.yl-4'-methylphenylhydrazide and 15.5 mg/100 cm2 of gelatin~
(3) An inter layer having the dry thickness of 1.0 ~m~
containing 6.0 mg/100 cm2 of 2,5~di-tert-octylhydrGquinone, 6.0 mg/100 cm2 of di n-butyl phthalate ~d 12.0 mg/100 cm2 ~.
of gelatin, (4) A layer having the dry thickness of 1.3 ~m, containing ~sstS~

1 10.O mg/100 cm2 of a magenta DRR compound having the following formulao OH C5Hll t CoNH(cH2)4o ~ C5H11 t l`~HS02~ ~
~IHCO~HCh~5 O
I OCH

OH ~2NH2 and 15.0 mg/100 cm2 of gelatin, (5) A layer having the dry thickness of 1.4 ~m, contain-ing 14.0 mg/100 cm2 (as silver amount) of a green light sensitive, internal latent image type silver iodobromide ~i emulsion, 1.0 mg/100 cm2 of potassium 2-octadecylhydro-quinone-5-sulfonate, 0.1~ mg/]OO cm2 of -formy]-4'-methylphenylhydrazide and 15.5 mg/100 cm2 of gelatin~
(6) An inter layer having the dry thickness of 1.0 ~m, containing 6.0 mg/100 cm2 of 2,5-di-tert oc-tylhydroquinone, 6.0 mg/100 cm2 of di-n-butyl phthalate and 12~0 mg/100 cm of gelatin, ~ ;~
(7) A layer having the dry thickness of 1.1 ~m, contain-ing 8.~ mg/100 cm2 of compound (61) and 12.5 mg/100 cm2 of gelatin, (8) A layer having the dry thickness of 105/,~m, contain-ing 140 5 mg/100 cm2 (as silver amo~mt) of a blue light sensitive, internal latent image type silver iodobromide emulsion, 0~7 mg/lOO cm2 of potassium 2-oc-tadecylhydro-quinone~5-sulfonate, 0~14 mg/lOO cm2 of formyl-4'~

- 108 ~

:~1557~
1 methylphenylhydrazide and 16.1 mg/100 cm2 of gelatin, and

(9) A protective layer having the dry thickness of 009 ~m, containlng 10.0 mg/100 cm2 of gelatin.
In the above-mentioned multi-laye~ed multicolor photosensitive element, the dispersion of the cyan DRR
compound, the magenta DRR compound and compound (61) was carried out in the following mannerD The cyan DRR
compound, the magenta compound or compound (61) was dissolved into acetone; the resulting solution was filtered to remove any insoluble into acetone; the resulting filtrate was poured into 125 ml of water to deposit the said compound 9 the deposit was collected by filtratlon and washed with water9 the aqueous slurry containing 7 wt. ~ of the cya~l DRR compound, the magenta DRR compound or compound (61) and 0.7 wt. ~o of Alkanol-XC was prepared9 and, the slurry was dispersed by means of a supersonic homegenizer in-to an aqueous gelatin solution.
Next, an image receiving element was prepared by successively forming the following layers on a transparent polyethyleneterephthalate film support having the thickness of about 100 ~mO
(1) A neutralizing layer having the dry thickness of 25 25.0 ~Im, containing 24.8 mg/100 cm2 of polyacrylic acid, (2) A timing layar having the dry thickness of 300 ~m, ``:
containing 5~0 mg/100 cm2 of cellulose acetate, and (3) An image receiving layer having the dry thicknes~ of about 200 ~m, containing 22.0 mg/100 cm2 of a copolymer of s-tyrene and N-benzyl-N,N-dimethyl-N-(3-Maleimidepropyl) ~5~ii'7~

1 ammonium chloride at the ratio of lol, aMd 22.0 mg/100 cm2 of gelatin.
The multi-layered multicolor photosensitive element thus prepared was exposed wedgewise through blue, green, red, yellow, magenta and cyan filters aMd -the~
superposed with the above-mentioned image receiving element, while a rupturable container containing 1.0 ml of an alkaline processing solution of the following composition was placed therebetween, thereby to form a photographic element.
Then, the above photographic element was passed through an opening of about 80 ~m between one pair of jux-taposed press rollers to rupture the container and spread its contents between the photosensitive element and the image receiving element.
Alkaline Processing Solutiono Potassium hydroxide 56 g Sodium sulfite 2.0 g l-Phenyl-3-pyrazolidone 8.0 g 5-Methylbenzotriazole 2.8 g ~;
TitaMium dioxide 40.0 g Sodium carboxymethylcellulose 50.0 g Distilled water to make up total 1000.0 ml After about 8-10 minutes, the good dye image was observed through the transparent support of the above-described image receiving elementO
~xample 3 A layered multicolor photosensitive and image receiving element was prepared by successively forming the following layers on a traMsparent polyethylene-5~'7~ ;

1 -terephthalate film support having the thickness of 100 t~m.
~1) An image receiving layer having the dry thickness of 2.0 ~m, containing 22 mg/100 cm2 o~ a copolymer of styrene and N-vinylbenzyl-N,~,N-trihexylammonium chloride at the ratio of 1 1, and 22 mg/100 cm2 of gelatin, (2) A light reflecting layer having the dry thick~ess of 7 ~m, containing 220 mg/100 cm2 of tita~ium dio~ide and 22 mg/100 cm2 o~ gela-tin, (3) An opacifying layer having the dry -thickness of 4 ~m, containing 20.5 mg/100 cm2 of carbon black and 42.0 mg/100 cm2 of gelatin, (4) A layer having -the dry thickness of 205 ~m, containing 14.3 mg/100 cm2 (as silver amount) of a red light sensitive, internal latent image type silver iodobromide emulsion, 0.7 mg/100 cm2 of potassium 2~
octadecylhydroquinone-5-sulfonate, 0.14 mg/100 cm2 of formyl-4'-methylphenylhydra~idel 800 mg/100 cm2 of a cyan DRR compound having the following formula OH a 5Hll-t = ~O~H(C~I2)40 ~ C5Hll-t ~IHS02~
So2NH~

02N~N=N~ OCOCH~
S02CH~

4.0 mg/100 cm2 of -tricresyl phosphate and 22.5 mg/100 cm2 of gelatin, ~ 111 -5~

1 (5) An inter layer having the dry thickness OL loO ~m9 containing 6.0 mg/100 cm~ of 2,5-di-tert octylhydro-~quinone, 6.0 mg/100 cm2 of di--n-butyl phthalate and 12.0 mg/100 cm2 of gelatin, (6) A layer having the dry thickness of 2.7 ~m, con-tain-ing 14.0 mg/100 cm' (as silver a~nount) o~ a green light sensitive internal latent image type silver iodobromide emulsion, 1.0 mg/100 cm2 of potassium 2~octadecylhydro-quinone-5-sul~onate, 0~13 mg/100 cm2 o~ formyl-4'- `

10 methylphenylhydrazide, 10.0 mg/100 cm2 of a magenta D~R
compound having the following formula ~;

OE ~5Hllt :~:
- CoNH(cH2)4o- ~ -C5Hllt NHS02~ .
~ N-N ~ -OCOOC2H5 CH~jS0 i~
5 0 mg/100 cm2 of tricresyl phosphate and 25.3 mg/100 cm2~-of gelatinj (7) An inter layer having the dry thickness of 1.0 ~m, : 15 containing 6.0 mg/100 cm2 of 2,5-di~tert-oc-tylhydroquinone, 6~0 mg/100 cm2 of di-n-butyl phthalateg 3.5 mg/100 cm2 of yellow colloidal silver and 1200 mg/100 cm2 of gelatin, (8) A layer having the dry -thickness of 2.7 ~m, ~;
containing 14~5 mg/100 cm2 (as silver amount) of a blue light sensitive9 internal latent image type silver iodobromide emulsion, 0 7 mg/100 cm2 of potassium 2-octadecylhydroquinone-5-sulfonate, 0l14 mg/100 cm2 of 5S7~

1 formyl-4' methylphenylhydrazide, 13.0 mg/100 cm2 o-f compound (1), 6.0 mg/100 cm2 of tricresyl phosphate and 26.0 mg/100 cm2 of gelatin, an~
(9) A protectiv~ layer having the dry thickness of 0.9 ~m, containing 10.0 mg/100 cm2 of gelatin.
The layers containing a cyan D~ compound9 a magenta DRR compound and compound (1) were formed in the following manner- The cyan D~ compound, the magenta DRR compound or compound (1) was dissolved into ethyl acetate and tricresyl phosphate 9 the resulting solution was dispersed in an aqueous gelatin solution containing Alkanol-XC (Du Pont de ~emours & CoO); on the other hand, the water-methanol (lol) solution of potassium 2-octadecylhydroquinone-5-sulfonate was dispersed into an aqueous gelatin solution containing Alkanol-XC; the dispersions thus obtained were mixed into the internal latent image type silver iodobromide emulsion containing a methanol solution of formyl~
methylhenylhydrazide just before -lhe coating was carried out.
Next, a cover sheet was prepared by successively forming the following layers on a transparent polyethylene-terephthalate film support having the thickness of 100 ~mO
(1) A neutralizing layer having the dry thickness of 25.0 ~m, containing 25.1 mg/100 cm2 of polyacrylic acid, and (2) A timin~ layer having the dry thickness of 3.0 ~m, containing of 5.5 mg/100 cm2 of cellulose acetateO
The layered multicolor photosensitive and image 1 receiving element thus prepared was exposed wedgewise through blue, green, red, yellow, magenta and cyan -~ilters and then superposed with the cover sheet, ~hile a rupturable container containing 1.0 ml of an alkaline ~;
processing solution having the composition set forth below, was placed therebetween~ thereby to form a photo-graphic element.
Then9 the above photographi.c element was passed through an opening of about 80 ~ between one pair of juxtaposed press rollers -to rupture the container and spread its conte~ts between the photo-sensitive and image receiving element and the cover ~.
sheet.
Alkaline Processing Solution~
Potassium hydroxide 56 g ; Sodium sulfite 2.0 g l-Phenyl-3-pyrazolidone 3~0 g 5-Methylbenzotriazole 2.8 g Carbon black (MA-100 by Mitsubishi Chemical Industries~ Ltd.) 100.0 g Sodium carbogymethylcellulose 50.0 g Benzylalcohol 10.0 ml ;~
Distilled water to make up total1000.0 ml hfter about 8 ~10 minutes, the good dye image was obser~ed through the transparent support of the above-mentioned photographic element~

- 114 - :

Claims (5)

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

1. A color diffusion transfer photographic element which comprises a silver halide emulsion layer and a yellow dye image-forming compound represented by the formula:

wherein A1' represents an aromatic hydrocarbon group or an aromatic heterocyclic group; R(1), R(2) and R(5) each represent hydrogen, halogen, nitro, an alkyl group, hydroxyl, alkoxy and aryloxy, a group of the formula -OCOY' (herein, the Y'CO- in the -OCOY' group represents a hydrolyzable group); R(3) is as defined with respect to R(1), R(2) and R(5), or the group , and R(4) represents the group , in which A3 is an aromatic hydrocarbon group or an aromatic heterocyclic group; X2 is a divalent joint group; Z' is hydrogen or the group YCO- (the YCO- is a hydrolyzable group);
M1 is a monovalent dye releasable group; X1 is a divalent joint group; q is 0 or 1; m is 0 or a positive integer; n is an integer not less than 1; r is 0 or 1; and w is an integer from 1 to 4.

2. A color diffusion transfer photographic element according to Claim 1 wherein at least one of R(1) R(2), R(3) and R(5) is hydroxyl, -OCOY1 or -OR(7) in which R(7) is an alkyl group or an aromatic hydrocarbon group.

3. A color diffusion transfer photographic element according to Claim 1 wherein the photographic element com-prises a photosensitive element having therein a support and said silver halide emulsion layer, the photosensitive element comprising the compound.

4. A color diffusion transfer photographic element according to Claim 2 wherein the photosensitive element further comprises a layer containing the compound whereby the compound is made present in the photosensitive element.

5. A color diffusion transfer photographic element according to Claim 2 wherein the photographic element com-prises a photosensitive element having therein a support and a silver halide emulsion layer containing the compound in which Z1 is the YCO group.