CA1117348A - Photographic film units containing a polymeric mordant which covalently bonds with certain dyes - Google Patents

Abstract

Abstract of the Disclosure A photographic element comprising a support, a layer containing certain photoographically useful and/or active fragments and a layer containing a dye mordant composition comprising a polymer having recurring units Or the formula selected from the group consisting Or:

and wherein:
R2 13 hydrogen or alkyl;
R1 is hydrogen> alkyl or aryl;
L is a linking group;
W is an electron-withdrawing group;
X is a leaving group; and n is 0 or 1.
The polymeric mordants covalently bond with dyes or dye precursors and are especially useful in d?ffusion transrer processes.

Description

The present invention relates to novel photographic elements containing polymeric compounds as dye mordants. ~ -It is known in the photographic art to use various polymeric materials and mordants in color image transfer elements comprising a support and layer generally containing a silver halide emulsion to prevent the migration of dyes or other photographically useful and/or active fragments.
~eceiving elements containing mordants are described3 for example, in U.S. Patents 2,584,0~0 and 3,770,1~39.
Many of the polymeric mordants described in -the prior art are quite useful in preventing migration of the ~ ;~
dyes from the mordanted layer. Polymeric mordants useful in this respect include those described in U.S. Patents 3,958,995, ;
3,')26,691l and the like. While nonionic, anionic and cationic polymers have been found to be satisfactory mordants for use ., , in image-transfer units~ it would be desirable to provide mordants which can better receive and hold dyes ~rom migration.
; It is an obJect of this invention to provide photographic elements containing polymeric mordants which `~ 20 have particularly strong holding properties with respect to '~ certain dyes.
It is a further object of this invention to provide a photographic element comprising a support, photographically useful and/or active fragments, a silver halide layer and at least one layer comprising a polymeric ~ mordant composition.
:- Still another object of this invention is to ` provide an integral image-transfer unit comprising a support~ ;
; at least one photosensitive silver halide emulsion layer ~ 30 having associated therewith certain dye image-providing .

-2-: ~ :

~ ~s ~3~

materia].s, and an image-receiving layer comprising a po1.y-meric mordant capable af covalently hon(ling with the dye.
i The~e o~jec1s are accompli.-he~l by 1.ncorporating in the el.ement, particular photographically useful and/or active fragments and particularly dye or dye precursors, and polymeric mordants which contain reactive groups which will covalently bond to the photographically use~ul and/or active fragments.
- The photographically useful or active fragment ;~
~ 10 (PUF) useful herein can be any nucleophilic fragment which is released in a photographic element preferably in an imagewise fashion. For example, the photographically useful group can be a photographic dye or dye precursor, or a photographic reagent such as a development inhibitor, a . development accelerator, a bleach inhibitor, a bleach accel-; erator, a coupler (e.g. a competing coupler, a color-forming coupler, a development inhibitor releasing coupler, etc.), :
a developing agent (e.g., a competing developing agent), a silver halide solvent, a silver complexing agent~ a fixing agent, a toner, a hardener, a fogging agent, an antifoggant, ~ a chemical or spectral sensitizer~ a desensitizer~ etc.
,~ The photographically useful group can be present .~ in the photographic element as a preformed species or it can be present in a blocked form or as a precursor.
`. The PUF materials of this invention can include a moiety which is an image-dye former. The term "image-dye rormer" is understood to re~er to those compoun(is which :~ undergo reactions encountered in a photographic imaging system to produce an image dye, such as color couplers, oxichromic compounds and the like.

_3_ , The PU~ materials described herein have particular application in a diffusion transfer process where it is desired to have a dye entity transferred to an adjacent layer or a receiving element~ However, in certain embodi-ments~ this invention relates to the release of an imagewise distribu-tion of a diffusible photographically useful com-pound which is a photographic reagent. Typical use~ul photographic reagents are known in the art, such as in U.S Patents 3,227,551, 3,698,898, 3,379,529 and 3,364,022, for example a silver complexing agent, a silver halide solvent, a fixing agent, a toner, a hardener, an antifoggant, a fogging agent~ a sensitizer, a desensitizer, a developer ;
or an oxidizing agent.
The photographically useful fragment can be a silver halide development inhibitor including triazoles and tetrazoles such as a 5-mercapto-l~phenyltetrazole, a 5-methylbenzotriazole, a 1~,5-dichlorobenzotriazole a~d the "; ~ .
~l like, and it can also be an antifoggant including azaindenes `' such as a tetrazaindene and the like. The compounds which ! 20 contain releasable silver halide development inhibitors or ~ antifoggants can generally be used in the photographic `; elements in association with silver halide layers wherein .. said compound can be incorporated in amounts such as 0.01 to , .
1 g/m disso]ved in a coupler solvent such as diethyl lauramide. When these compounds are incorporated in photographic elements in association with negative silver halide emulsions, a positive imagewise distribution of inhibitor or antifoggant will be produced upon development if released from a positive-working carrier. Thus, silver ,, ~ 30 development is inhibited or restrained in the low-exposure :

' ' ':, ~ : ~ ... . ,~

toe but not in the shoulder as seen on the sensitometric curve. 'I-eve'lopment inhi'bition of the unexposed areas is thereby achieved selectively. When the si~lver halide emulsions also have dye releasers in accordance with this invention associated therewithg the overall effect of -the -inhibitor or antifoggant is to release more dye in the unexposed regions, improving maximum image dye density to the image receiving layer without increasing the amount of dye released in the exposed regions.
The photographically useful fragment can also `~ be a silver halide development accelerator such as nucleo-phi'lic substituted benzyl alcohol, benzylpicolinium bromide, ~ foggants including hydrazines and hydrazides such as an N-^~ acetyl N'-phenylhydrazine and the like, or auxiliary developers ;~
such as hydroquinones, a l-phenyl-3-pyrazolidone, an ascorbic ' acid and the like. When -these compolmds are used in photo-graphic elements in association with negative silver halide emulsions which also have associated therewith positive-working image dye-providing materials in accordance with this inventiong the released dye density of all dyes in the unexposed regions would be somewhat reduced by fog development.
'~ If, however, one layer was unexposed while the other two were given an imagewise exposure, the amount of foggant or development accelerator reaching the unexposed layer from the other two layers would be less where those layers were ;~
exposed. Hence, the ~max of the unexposed layer would increase as a function of exposure of~the other two layers.
This greatly enhances the saturation of single colors in a photograph.
When color couplers are present in the compounds of this invention, the coupler can be released in areas ~. ' :

'7 ~

where no development occurs and can diffuse to an adjacent layer where they can be reacted with an oxidized color developer such as a primary aromatic amine to form the image dye. Generally, the color coupler and the color developer are so chosen that the reaction product is immobile.
Typical useful color couplers include the pyrazolone couplers, pyrazolotriazole couplers, open-chain ketomethylene couplers, phenolic couplers and the like. Further reference to the description of appropriate couplers is found in Marchant, U.S. Patent 3,620,747 issued November 16~ 1971.

The fragments containing oxichromic moieties can also be advantageously used in a photographic system since . ' ,.
they are generally colorless materials due to the absence i~ of an image-dye chromophore. Thus, they can also be used directly in the photographic emulsion or on the side of the film unit through which exposure takes place without compe-titive absorp-tion. Compounds of this type are those compounds which undergo chromogenic oxidation to form the respective :~ 20 image dyes. The oxidation can be carried out by aerial ~ ~, `' oxidation, incorporation of oxidants into the photographic element or film unit, or use of an oxidant during processing.
. .~
Compounds of this type have been referred to in the art as leuco compounds, i.e., compounds which have no color. Typical useful oxichromic compounds include leuco indoanilines, leuco indophenols, leuco anthraquinones and the like. In certain preferred embodiments~ the compounds of this invention contain oxichromic moieties as descri~ed in Lestina and Bush, U.S. Patent 3,8803658.

c.~

7~

The particular PUF materials including dyes, dye precursors or dyes released from dye-providing compounds useful in t~lis invention are those having appended thereto a moiety selected from the group consisting of aminoalkyl preferably having the formula ZNHR, sulfonamido preferably having the formula -SO2NH and phenolic preferably R
having the formula o~

wherein R is H or alkyl, preferably containing from about 1 to about 6 carbon atoms such as ethyl, methyl, isopropyl, chlorobutyl and the like. Z is an alkylene or cycloalkylene group preferably containing from 1 to 6 carbon atoms such as "
methylene, ethylene, cyclohexylene, and the like or arylene-alkylene such as phenylenemethylene and Z and R can be taken together with the NH to complete an N containing heterocycli.c group preferably contalning from 5 to 7 carbon atoms. Dyes, dye precursors and dyes released from dye-providing materials containing these groups are preferred and are well known to , .
those skilled in the art.
Examples of dyes or dye precursors containing the ZNHR groups are amine dyes such as Cl ' CH CH
HN(CH2)2NS02-0~ ~o-N=N-~ e-OH

., SO NHCH
:. 2 3 ~ SO NIIC(C~I ) .~ 1 2 3 3 HN\ S /o-CH2NHSO2-~ -N=N-~ ~-OH

C H 3 S 2 N H ~

~: -7-,' " ~ ::

HN(CH2)2NS02 ~--99 SO2NH~
NO2 o~ ~--N=N-~ ~a-OH
,,,_~, o=~

~' ;~ Examples of those dyes or dye precursors con~
taining -S02N~ groups are sulfonamido dyes such as:

~ N---N
, \ / ~ ,, N=N-~-S02NH2 ,

3~ ~--N---N
~=~ o=~ -CN

=N-~ ~9SO2NHz `~
SO2NH-~

OH
~ -SO2NHC(CH3)3 CH3SOzNH N=N-~ ~3-SO2NH2 , ~_ ~
:'` 0~1 `n' I

~ o-so2NH N=N-~ ~9-NO2 ;`
and the like.

. 8 .
' ~

~ J~ ~ ~

Examples of those dyes or dye precursors con-tairling:

~o~
\o=~OH

: groups are phenol dyes such as: ;

OH o o~ NHSOz-0~ ~o N N /~-N-o\
= 9 / \ t = N ~r -NHS02-~\ /o-CI SOaNHCH3 OH N=N-~ a-OH
':~' C I , ,:
~: SO2NHC2Hs - N H S O a- ~ -N-N-~ OH
a= ~ /~3= ~
OH CH 3 S O a NH~ o : NO2 ; H ~~--NHS02-0~ ~o C I
;~ O H N_N-3~ ~3-OH
CHoNHSO2-~ ~0 ~:.
:~: and the like.
, "~
.: 10 In general, image dye precursors are those materials ~:
which contain the chromophore of the desired image dye in a latent state~ including, for example colorless compounds such . . .
as leuco dyes that are converted to image dyes by oxidation, ~`
:~ and shifted dyes which are initially colored but whose maximum absorption can be shifted to the desired image hue by chemical 3 means such as hydrolysis, pH change~ etc.

:, --9--.':
,: . . . ,.

., - ,. , , , .:

Any of the dyes or dye precursors can be released from dye-providing compounds such as those described in Fleckenstein U.S. Patent No. 4~076,529 issued February 28, ~ 1978.
~ The polymeric mordants useful in this invention to :
: bond covalently with the classes of PUFs described above are ::: nonionic~ anionic or cationic homopolymers or copolymers ,,. :
~` containing recurring units having the formula selected from the group consisting of:
.
'.,~ R2 R2 , t t .-1) ~CH2-C~ and 2) ~CH2-C~

(L)n , (,)n , wherein R is hydrogen or alkyl; n = 0 or 1; Rl is hydrogen, .~ alkyl or aryl; L is a bivalent linking group providing a .. :
`i linkage between the vinyl group and W; W is an electron-~ withdrawing group and X is a leaving group which can be ;~ displaced by a nucleophile or eliminated in the form of ;~; HX by treatment with alkali; said PUF material and said recurring lmits forming a covalent bond on contact.

When R2 is alkyl, it preferably contains from .:` 1 to 6 carbon atoms such as methyl, ethyl and the :

- 20 like. :
~:-. Rl can be hydrogen, alkyl preferably containing-from 1 to 12 carbon atoms as dèscribed above for R2, or aryl preferably containing from 6 to 13 carbon atoms such ;;~ as phenyl, naphthyl, tolyl, xylyl and the like.
It is understood that~ wherever alkyl, aryl or - alkylene is described in the specification, the terms are :~
.
'"'''~ ~' -10-,.:, ;; ' ' ' ' . ` ' - ~ ' . , :

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

meant to include isomers thereof and substituted alk~l, aryl or alkylene wherein the substituent does not adversely affect the covalent bonding of the dye to the polymer.
The linking group ~ can be selected from the group consisting of alkyleneg preferably containing from about 1 to about 6 carbon atoms such as methylene~ isopropylene, hexylene and the like; arylene preferably containing from about 6 to about 10 carbon atoms such as phenylene, naphthalene - and the like; arylenealkylene preferably containing from about 7 to about 11 carbon atoms such as benzyl; CooR3; and CoNHR3 wherein R3 is selected from the group consisting of arylene, alkylene or arylenealkylene such as described ; above.
X is a leaving group which can be displaced by elimination in the form of ~ under alkaline conditions such as hydro~y, chloro, bromo, iodo,, alkyl and arylsul-fonylo~y (-OS02R'), ammonio, sulfato (-OS03-), and the like.
The electron withdrawing group W stabilizes an a-carbanion which facilitates the elimination of HX resultingin an electron deficient double bond. W can be selected from the group consisting of -S02-, -C0-, -S0-~ -OC-, "~' ` R l O
~NC~m and -NS02-, wherein m is 1 or 2 and R is as described ~ above. 0 ; When n = 0 in formulas 1) or 2) then W is -S02- or -OC-. ;

~ highly preferred class of polymers according to the structure described above has repeating units having the ;` formulae:
~. ~
',, -11-~, .

.... .

3~

~C~i2 C~ or ~CH2-C~

n x 1 (L)n S02CH2 CH S02CH=CHR

wherein Rl, R2, L, n and X are as described above. Examples of these polymers are poly(vinylbenzyl 2-chloroethyl sulfone), poly(vinylbenzyl vlnyl sulrone) and the like. A description Or the preparation of these polymers can be round in U,S. Patent 4,161,407~ issued July 17, 1979, by Campbell entitled "Crosslinkable Rolymers Having Vinylsulfonyl Groups or Styrylsulfonyl Groups and Their Use as Hardeners ~or Gelatin."

Another preferred class of polymers are those con-taining repeatlng units havlng the formulas:

~CH2-C~ O O X
tL)n-NHC~ HC-CH2-CHR or . .
R2 ,.
: ~CH2-C~ 0 O .
.. , " "
`~. (L)n-NHC NHCCH=CHR

`:~; wherein Rl, R2, L, n and X are as described above. Examples of these polymers are poly~N~2-methacryloyloxyethyl)-N'-(3~
chloropropionyl)urea] and poly[N-~2-methacryloyloxyethyl~N'-.. , ' ~ (acryloyl)urea3~ and the llke. These polymers can be prepared .. ~. by free radical polymerizatlon of the corresponding chloroethyl monomer rollowed by dehydrohalogenation of the resulting i .
polymer.
Another pre~erred class of polymers are those containing recurring unlts havlng the formulae:

. ~

~ ~12-/ ' ;,. R2 R2 ~ ~CH2 C~ X , or ~CH2-C~ 0 (L)n-NHC-CH2-CHR L(n~-NHC-CH=CHR

- wherein Rl, R2, L, X, and n are as described above.
The polymers containing the recurring units described above preferably comprise anionic, cationic or nonionic polymers comprised of the above units and units derived from copolymerizable ethylenically unsaturated monomers. Although ; the preferre~ copolymerizable monomers form units which aet as mordants for dyes in themselves, basieally any polymerizable monomer may be used to form the polymeric mordant.
~; , Cationic polymers can be formed by copolymerizing ,;; ., monomers ~ormlng the units described above in formulas (1) and ~;

(2) and monomers whieh form repeating units sueh as:
~CH2 1 ~

~aXcH2-Q-R M-~` R

i wherein Q is N or P, R4 to R6 are independently earboeyelie or 3 alkyl groups, and M is an anion sueh as deseribed in U.S.

`~I Patent 3,958,995, and other cationic units sueh as N-~`I (methacryloyloxyethyl)-N,N,N-trimethylammonium methosulfate, N-(methacryloaminopropyl)-N,N,N-trimethylammonium chloride, ~ .
~ and the like.

; 20 Anionic polymers can be formed by copolymerizing ;~ with the monomers forming the units deseribed in formulas , (1) and (2), monomers whieh form repeating units sueh as ~ sodium-2-sulfoethyl methaerylate, sodium 2-acrylamido-2-sj methylpropanesulfonate, sodium vinylbenzylsulfonate, sodium ?' "~

vinylbenzenesulfonate, and the like.

", ~' ' ' . ' , 3'~

Nonionic polymers can be formed by copolymerizing with the units of forMulas (1) and (2), monomers which form repeating units such as acrylamide, N-vinylpyrrolidinone, N-isopropylacrylamide, and the like.
The polymers can be either homopolymers having the repeating units of formulas (I) and (2) or copolymers of these with other cationic, anionic or nonionic ethylenically .~ unsaturated monomers. Preferred cationic copolymers are poly[m and ~-vinylbenzyltrimethylammonium chloride-co _ and ~-vinylbenzyl 2-chloroethyl sulfone] (1:1 w) and poly[m and p-vinylbenzyltrimethylammonium chloride-co-m and _-vinylbenzyl vinyl sulfone-co-divinylbenzene] (49:49:2 w). A preferred ~
anionic copolymer is poly[m and _-vinylbenzyl 2-chloroethyl ~ -sulfone-co-sodium 2-sulfoethyl methacrylate] (1:1 w).
A preferred nonionic copolymer is poly[acrylamide-co-,.:
vinylbenzyl 2-chloroethyl sulfone] (80:20 w). Preferably~
the copolymers comprise from about 10 to about 90 weight percent of the repeating units of formulas (1) and (2).
~he homopolymers or copolymers can be formed by free .; .
radlcal polymerization of the corresponding monomers and by optionally treating the resulting polymers with alkali.
It has been found that certain of the polymers are more likely to ~orm covalent bonds with certain dyes, thus forming especially strong bonds with said dyes in the image-receiving layer. ~hus, the polymers containing recurring units having the formulae:

' ~CH2-C~ ~CH2 C~

S02-CH2-CHRl S02-CH=CHR

.,` .:
: -14-,,' ,; .

3~

covalently bond with the PUF materials containing as sub-stituents (having appended thereto) ZNHR groups when the polymer is anionic, and provides covalent bonds with PUF
materials having appended thereto ZNHR, -S02NHR or:

' \ - XOH

: when the polymer is cationic or nonionic.
;, It has also been found that polymers containing the .~ recurring units having the formulae: ~

R2 ~:
~CH2--C~ O O X ;
~ (L)n-NHC NHC-CH2-CHR
:~ 10 or ~' 2 ~ . :
,;;,~ ~CH2-C~ O O ~
~'' (L)n NHC NHC-CH=CHR
~.,`,1 .~ '.`~

`',!covalently bond with PUF materials having appended thereto ~ZNHR when the polymer is cationic or nonionic, and will i-,covalently bond with dye or dye precursors having appended ~;

.thereto ZNHR, -S02NHP~ or: -,'`- -\ X ': -,~ ~
.uwhen the polymer is cationic.

. Polymers~containing the recurring units having the ,~
~ formula: i.- ;. -. . .
. R R2 X o r :. 20 ~C~I2-C~ ,, ~ 1 ~CH2-C~ O
~ (L)n-NHC-CH2-C~ (L)n-NHC-CH=CHR
. .

.~.",~ .
, -15-~.
. . .
.- . .
: ~ , , . ~, I, ,, :
- . . ~ . .. . , ; .

\
3~ -, .

provide covalent bonds with P~F materials having appended thereto ZNHR when the polymer is cationic.
- A simple test may be used to determine if the polymer and dye or dye-providing material form a covalent bond on contact. ~`
The test comprises:
a) preparing a dye-receiving element by coating a poly-(ethylene terephthalate) film support with a layer `
comprising gelatin at 2.16 g/m2, a divinylsulfonyl " , ether hardener at 0.04 g/m', and the polymeric mor-dant at 5.5 millimoles/m2 of reactive unit of formulas (1) or (2); ; ~9 b) immersing separate samples of receiving element in 1.0 ~ `
percent by weight aqueous solution of the dye for up to 10 minutes, washing in water for 20 minutes and air-drying; and ;~
;' c) measuring the dye density at maximum absorption and ; determining the percentage of covalent bonding from the dye density lost after subsequent treatment of each sample for 2 minutes in a solvent mixture consisting of 200 ml of methanol, 200 ml of CH2C12, 20 ml of water and 10 g ;~
NH4SCN, which solvent removes substantially all dye not -~ covalently bonded. The percentage of dye or dye precursor ! `
- covalently bonded to the polymer should be at least 5% and .~, preferably 50 to 100%.
, .
~ The dye mordant composition is quite useful in the ;~
-~ preparation of photographic elements comprising a support and at least one layer comprising a dye mordant and at least ~ one layer comprising a dye or dye precursor. The support can ~ ~
`~ comprise any photographic support material such as paper, `
baryta-coated paper, resin-coated paper, pigment-coated polymeric film, poly(ethylene terephthalate), cellulose acetate, glass, ,'` ` ~

,: ' ` ' :

; grained aluminum, polycarbonates and the like such as des-cribed in Product Licensing Index, Vol. 92, Dec., 1971, - publication 9232, pp. 107-110. ~he support can consist of any of the above materials or like materials coated with various layers such as timing layers, overcoat layers, acid layers and the like. The support is coated with a substantially aqueous dispersion of the polymer according to the invention, and thereafter the layer or layers containing the dyes or dye precursors are applied.
In a highly preferred embodiment, this invention relates to image-transfer film units comprising~
a) a photosensitive element comprising a support having ~ thereon at least one layer containing a silver halide :~l emulsion having associated therewith an image dye-`¢ providing material containing or which releases a ,`~1 moiety containing the ZNHR, ~S02NHR or .~:. \ X
., .

moieties;
b) an image-receiving layer containing the above-described ;
mordants; and ;~ c) means containing an alkaline processing composition adapted ~; to discharge its contents within said film unit.
~',! Mordanting amounts of the polymers according to this invention can be employed as such from a substantially ,~ aqueous medium or can be incorporated in water-permeable hydrophilic organic colloid binders and the resulting mixture used in the preparation of dye imbibition printing blanks, receiving layers for color-transfer processes such as those ,, .
described by U.S. Patents 3,362,819 by Land, 2,983,606 by 3 Rogers, 3,227,552 by Whitm,ore and 3,227,550, and in antihalation layers such as those described by Jones et al, U.S. Patent . .
:,~, ., ;, . .:
; :: ~ , ~

3 ~

3,282,699. Satisfactory colloids which can be used ~or this purpose lnclude any of` the hydrophilic colloids generally employed in the photographic field including, for example gelatin, colloidal albumin, polysaccharides, cellulose deriva-tives, synthetic resins such as polyvinyl compounds, including polyvinyl alcohol derivatives, acrylamide polymers and the like.
In general, a mordanting amount can be employed in a dye-mordanting or dye image-receiving layer. The amount of dye mordant to be used depends on the amount of dye to be mordanted, the mordanting polymers, the imaging chemistry involved, etc.
The amount can be determined easily by one skilled in the art. The dye image-receiving element can comprise a support ; having the polymeric mordant of this invention thereon. The element may also comprise other layers such as a polymeric acid layer and can also include a timing layer as taught in U.S. Patent 2,584,030 and disclosed in U.S. Patent 3,362,819 or a light-reflective interlayer comprising a light-ref-lective ~, white pigment such as TiO2 and the polymeric binder in accordance with the teaching of Beavers and Bush, U.S.

Patent 3,4l15,228.
The mordanting polymers according to this inven-tion are also especially use~ul in light-filtering layers such as in antihalation layers of the type disclosed by Jones and Milton, U.S. Patent 3,282,699. Here, the light-filtering layer preferably can comprise a hydrophilic col-loid and the polymer of this invention. The layer is adapted ~, to contain a dye held or fixed by the mordant. -~
In certain preferred embodiments, the mordants of this invention are employed in image-transfer ~ilm units to ~; 30 mordant the image dye. The mordants can generally be used in any image-transfer film unit format where initially mobile compounds are used~ such as dye developers, or where .

" ^

!

7~3r~ .
-initially immobile compounds are used, such as compounds which release a diffusible dye as a function of oxidation of the compound. Typical useful image-transfer formats are disclosed in U.S. Patents 2,432,181, 2,983,606, 3,227,550, 3,227,552, 3,415,645, 3,415,644, 3,415,646 and 3,635,707, Canadian Patent 674,082 and Belgian Patents 757,959 and ~57,960, both issued April 23, 1971. ln highly preferred embodiments, the mordants of this invention are used in the -~ photographic element of an image-transfer film unit which is -! 10 designed to be processed with a single processing solution, and the resulting positive image is viewed through a trans-: .:
parent support and against an opaque background.

In highly preferred embodiments, the mordants of ~ `~
thls invention are useful in color image-transfer film units which comprise:
j :
;~ a) a photosensitive element comprising a support having ~
`~! thereon at least one layer containing a silver halide ~;
-1 emulsion havlng associated therewith an image dye-providing material and preferably three of said layers which contain, respectivelyg a blue-sensitive silver ;i halide emulsion, a green-sensitive silver halide emul-sion and a red-sensitive silver halide emulsion;
b) an image-receiving layer containing the mordants of the above formula which can be located on a separate sup-port and superposed on said support containing said ~ silver halide emulsion layers or, preferably, it can be `~ coated on the same support ad~acent the photosensitive silver halide emulsion layers; and c) means containing an alkaline processing composition 3 adapted to discharge its contents within said film unit.

''' 19 .. ~ :
: '-,:~ ~ , : ,.~ ::.. .:.
.. ,. :

'73~
Where the receiver layex is coated on the same support with the photosensitive silver halide layers, the support is preferably a transparent support, a reflecting layer and opaque layer are preferably positioned between the image-receiving layer and the photosensitive silver halide layer, and the alkaline processing composition preferably contains an opacifying substance such as carbon or a combination of a p~-indicator dye and a pigment such as TiO2 which i5 discharged into the film unit between a dimensionally stable support or cover sheet and the photosensitive element.
In certain embodiments, the covex sheet can be supex~
posed or adapted to be superposed on the photosensitive element.
` The mordant layer can be located on the cover sheet. In certain ~ preferred embodiments where the image-receiving layer is located '! in the photosensitive element, a neutralizing layer is located on the cover sheet.
;~ A means for containing the alkaline processing solu~
i "
tion can be any means known in the art for this purpose~ including `~ rupturable containers positioned at the point of desired discharge of its contents into the film unit and adapted to be passed be-tween a pair of juxtaposed rollers to effect discharge of the contents into the film unit, frangible containers positioned over or within the photosensitive element, hypodermic syringes/ and the like.
The term "image dye-providing material" as used herein is understood to refer to those compounds which either do not require a chemical reaction to form the image dye or undergo re-actions encountered in photographic imaging systems to produce an image dye, such as with color couplers, oxichromic compounds (leuco dyes), pre-formed dyes including indicator dyes, shifted dyes, and the like.

:' - `
~ ~73~8 The terms "initially diffusible" and "initially immobile" as used herein refer to compounds which are incor-porated in the photographic element and, upon contact with an alkaline processing solution, are substantially dif~usl-ble or substantially immobile, respectively.
The image dye-providing materials, in one embodi-ment where negative silver halide emulsions are used, can be initially mobile image dye-providing materials such as those used in image-transfer photographic elements. Typical useful, initially mobile image dye-providing materials include dye developers as disclosed in U.S. Patents 2,983,606, 3,255,001 and the like; oxichromic developers which undergo chromogenic oxidation to form image dyes as disclosed in U.S. Patent No. 3,880,658; shifted indophenol dye developers as disclosed by Bush and Reardon, U.S. Patent No. 3~854,985;
metallized dye developers as disclosed in U.S. Patents 3,482,972, 3,544,545, 3,511,406 and 3,563,739; and the like.
The image dye-providing material in another 2~ preferred embodiment, especially when negative silver halide emulsions are used, is an initially immobile image dye-"j~ . .
providing material. Preferably, the initially immobileimage dye-providing material is a positive-working immobile photographic compound such as disclosed by Hinshaw and Condit, British Patent 1,464,1O4 and U.S. Patent 3,980,479.

Other especially preferred image dye-providing materials for use with negative emulsions to produce positive dye images are the quinonyl carbonates, quinonylmethyl carbonates, ! ;'`, .

` .
, 3 ~

and ~-nitro-arylcarboxamides described in Chasman, Dunlap and Hinshaw, U.S. Patent No. 4~139,379 issued February 13, In another embodiment, lmmobile image dye-pro~ldlng compounds can be used in assoclation with silver hallde emulsions wherein sald compounds undergo oxidation ~ollowed - by hydrolysi~ to provide an imagewise distribution Or a moblie image dye. Compounds of thls type can be used with negative emulsions to form posltlve image records ln the exposed photo-graphic element, or they can be used with direct-positive or reversal emulsions to form positive transfer images such as in an image-transfer film unlt. Typical useful compounds of this type are disclosed ln Canadian Patent 602,607 by Whitmore et al issued August 2, 1960, U.S. Patent 4,076,529 by Fleckenstein et al issued February 2B,1978, U.S. Patents 3~698,897 by Gompf et al, 3,928,312 by Fleckenstein, 3l728,113 by ~ecker et al, 3~725,062 by Anderson et al, 3,227,552 by Whltmore, 3,443~939, 3,443,940 and 3,443,941 and the like.
:

In highly preferred embodiments, the mordants of the above formula are used in image-transfer film unlts which also contain an immobile image dye-proYidln~ material which releases a sulfonamido dye as a ~unctlon of oxidation. Typical useful materials which release sul~onamldo dyes as a function Or oxldation followed by hydrolysls are disclosed by Fleckenstein et al, U.S~ Patent No. 4,07S,529.

In still other embodlments, the above mordants can be us~d ln lmage-transfer ~ilm unlts contalning a layer comprlsing a negative silver halide emulsion and having an adJacent layer containing physical development nuclei asso-ciated with an image dye-providing material. Typical photo-graph~c elements of this type are disclosed in U.S. Patent 3,227,551 (col. 6-7) and British Patent 904,364 (p. 19).

~ ~:
The dye image-providing material need only have appended thereto a moiety selected from the group consisting of ZNHR, -S02NHR and:

o=~ OH

where R and Z are as described above. The sulfonamidophenol dye releasers described by Fleckenstein et al in U.S. Patent No. ~,076,529, can be prepared con-taining the moieties described above by the methods described in U.S. Patent No. 4,076,5Z9.
The mordants can also be used for fixing the dyes used in the preparation of photographic filter, antihalation and gelatino-silver-halide emulsion layers. Such layers can be coated on cbnventional photographic supports9 such as flexible sheet supports (e.g. cellulose acetate, polyester films~ polyvinyl resins, etc.) or paper, glass~ etc.
More than one of the mordanting polymers of this -~
invention can be used together, in a single layer or in two or more layers. The mordantin~ polymers of this invention can also be used in admixture with other mordants in the same layer or in separate layers of the same element.
It is noted herein that the term "in reactlve association with" is intended to mean that the materials can be in either the same or different layers so long as the materials can perform reactive functions with each other.

`~ ~f -23-r , ' .', .'' : ' ` ' 3~, In an image-transfer unit containlng the dye or dye precursors and the polymeric mordants of this invention, a color image can be transferred to an image-receiving layer by using a ~ilm unit comprising a transparent support coated with the image-receiving layer containing the polymeric mordants, an opaque light-reflective layer, a black opaque layer and photosensitive layers having associated therewith dye image-providing materials containing the groups capable of rorming covalent bonds w~th the polymer mordants. A
rupturable container containing an alkaline processing composition and an opacifier such as carbon black is posi-tioned adjacent the top layer and a transparent cover sheet.
The cover sheet can comprise a transparent support ~hich is coated with a neutralizing layer and a timing layer. The film unit is placed in a camera, exposed through the trans-parent cover sheet, and then passed through a pair o~
pressure-applying members in the camera as it is being removed therefrom. The pressure-applying members rupture the container and spread processing composition and opaci-f'ier over the image-~orming portion o~ the film unit. The silver halide layers are developed and dye images are formed .: .
as a function o~ development. The dyes dif~use to the image-receiving layer to provide an image which is viewed through the transparent support on the opaqùe reflecting layer background. The timing layers break down after a perlod of time and make available materials to neutralize the alkaline processing composition and to shut down further silver halide development~

Various other processes can also be used to produce images using the units Or this invention. For instance, ' ~, ' ., ` ~ ~ .

3r~l~

transparencies can be made by retaining the element containing ; the photosensitlve layers after exposure and processing. The dyes in the non-image areas would be transferred to the mordant and the unit could be peeled apart to reveal the retained dye image in the photosensitive element. Reflective prints can ~^ also be prepared in somewhat the same manner.
The following examples further illustrate the invention.

Pre~aration 1: Poly(vinylbenzyltrimethylammonium chlo-; 10 ride-co-vinylbenzyl 2-chloroethyl sul-` fone) (1:1 w) , A solution of 30 g of m~p-vinylbenzyltrimeth~
` ylammonium chloride, 30 g of m~p-vinylbenzyl 2-chloroethyl sulfone and 300 mg of 2,2'-azobis(2-methylpropionitrile) in ~ 21l0 ml Or dimethyl sulfoxide was flushed with nitrogen and ,`'!~ heated at 60C overnight. The polymer was isolated by , i, . - , li precipitation in acetone, collected by filtration, washed - , ~
~, with acetone and dried in vacuo at room temperature. Yield =

58.ll g.

20 Anal. Found: C, 57.5; H, 7.0; C1, 13.7; S 5.0; N, 3.1.
[n]0 lN NaCl Example 1:

The cationic polymer of Preparation 1 having the ':
`~ structure:

CH2-CHt---------------~CH2-CH3 ~ .,.

CH2N (CH3)3 CH2~02CH2CH2CI :
Cl ~
'' ~ .,, ; was used in a mordant layer and its mordanting properties to a dye according to the invention was compared with that of a similar conventional cationic polymeric mordant having the structure:

:

.:, ., ,,"' .

~ `
:
3~3 ~CH2-CH~-~CH2-C~
I~ `n I~ `~ c~
'~ CH2N ( n-hexY I ) 3 as described in U.S. Patent 3,898,o88 to the same dye.
A dye image-receiving element (Element A) was prepared comprising a transparent poly(ethylene terephthalate) film support having coated thereon (1) a layer containing the polymer of Preparation 1 at 200 mg/ft2 (2.16 g/m2) and gelatin at 200 mg/ft2 (2.16 g/m2), 2 ~ ~
` (2) a layer containing gelatin at 50 mg/ft (0.54 -`~ lO g/m ) and a bis(vinylsulfonylmethyl) ether ~,~
hardener, and (3) a reflecting layer containing titanium dioxide at 200 mg/ft2 (2.16 g/m2) and gelatin at ~-200 mg/ft2 (2.16 g/m2).
A second receiving element (Element B) was prepared as above, except that the polyMer of Preparation 1 was replaced with an equivalent amount of the prior art control ~ -. mordant described above. ' 'ii The mordants were then evaluated by transferring a dye from a photographic element comprising a negative-working silver halide emulsion and a redox dye-releasing compound having the structure:

.-,' :; .:

.
' "~

' -26-~ .
.,~ ., .. . . .
: .
. .

' oco ~ ~ o \2=~/ .
~-CN OH
o N=N-~
C H C H
SO NCH2CH N-C=O CHs O ~ N~
s7 1 C
3 o ~ .

by rupturing a pod containing 56 g/1 potassium hydroxide, 23 g/l potassium bromide and 25 g/l hydroxyethyl cellulose between samples of the photographic element and either Element A or Element B. Because the redox dye-releasing compound is designed to release a diffusible yellow dye under alkaline conditions in the absence of an oxidized, ~;
crossoxidizing developing agent, a un:lform distribution of yellow dye was transferred to the receiving element. The elements were separated after 5 minutes and the receiving elements were washed for about 5 minutes. `~
The receiving elements which contain the yellow dye (hereinafter denoted as the senders) were then brought . . ~
-`~ in contact with additional samples of either Elements A or ~ ;

B which did not contain dye (hereinafter denoted as the - receivers) while rupturing a pod between the two mordant-containing elements which contained a viscous buffering ;~ solution comprising 23 g/l potassium bromide and 23 g/l !''~ hydroxyethyl cellulose dissolved in 1 liter of a pH 5 phosphate buffer. The elements were left laminated and the ' mordant competition was evaluated by the amount of dye . .

i, transferred from the sender to the receiver 12 hours after lamination, as measured by the reflection density to blue light from both sides of the laminated structure. Table 1 below records the mordant competition values, measured as the ratio of reflection denslty between combinations of Elements A and B acting as the sender and receiver.

; Table 1 Competition `
Sender/Receiver Ratio~
10 Element Mordant A/B Preparation l/prior art 2.18 B/A prior art/Preparation 1 (2.43) A/A Preparation l/Preparation 1 23.5 ~reflection density to blue light as measured in the sender divided by the reflection density as measured in the receiver after 12 hours lami-nation It is apparent from the above results that, when , .
the yellow dye was transferred at pH 14 to a mordant receiver ` 20 containing the mordant of the instant application, quanti-tative covalent bonding was obtained as demonstrated by the failure of consecutive relaminations at pH 5 with the prior art and Preparation 1 receivers to remove the dye from the sender. On the other hand, the Preparation 1 receiver removes the dye nearly quantitatively from the prior art receiver at pH 5.
Further evidence of covalent bonding was obtained when the dye could not be removed from the Preparation 1 containing element with a 2% solution of thiocyanate ion 30 in CH30H/CH2C12 (50:50 by volume), a treatment which rapidly removed the dye from the prior art mordant-containing element.

It was further found that the polymeric mordant of the instant lnvention was stable even after being subJected to severe keeping conditions.
` ,.
~ Example 2: -:
:: .
This is a comparative example.
Cationic mordants containing reactive sites are reacted with the list of Technicolor dyes described as being useful with polymeric mordants in U.S. Patent 3,625,694 to `~
determlne if they covalently bonded with said dyes, as follows:
Dye-receiving elements were prepared by coating a ~ . .
` poly(ethylene terephthalate) film support with a layer -~' comprising gelatin at 200 mg/ft2 (2.16 g/m2), a bis(vinyl-sulfonylethyl) ether hardener at 4.0 mg/ft2 (0.04 g/m2) and `~
a mordant (see Table 2) at 0.51 mmoles of reactive site/ft2 -;
, (5O5 mmoles/m2). `~
? Separate samples of each receiving element were then immersed in 1.0% aqueous solutions of the dyes listed in Table 2 for 1-10 minutes, washed for 20 minutes and air-dried.
The dye density at maximum absorption (~max) was then measured and the percent of covalent bondin~ was estimated ;i from the dye density lost after subsequent treatment of :~: .
~' each sample for 2 minutes in an organic solvent mixture ', consisting of 200 ml methanol, 200 ml CHC12, 20 ml H20 and 10 g NH4SCN. This organic solvent mixture was formu-lated to remove substantially all dye which was not covalently bonded. After treatment with solvent, the samples were washed in water for 20 minutes and air-dried.
The results are tabulated in Table 2.

~ ~ ~7~

r~
~1 ~1 ~ O O O O O O O O O O O O
O
C~
O
~ m . ~ r~ L~ O ~O ~O ~O ~O ~O ~O ~O
' ~
O~ ~ O O ~CO ~ 0 ~1 ~O ~ O
U~ ~ ~ t--~ O ~ CO ~ L
' (L) ~1 1~ l ~1 0 0 0 ., ~
. . ~r_r~_~
.
bO ~
~ ~ ~O ~r ~o ~ ~ :
:' ~
O
.'' ~ 0 0 ~0 . ~ ~, m ~ ~ cC m c~ ~ ~ m .; ~ O O O
~, : a~
.. ~
~1 ., ~ ..
~/\
. I 11 . ~ 0 ~, ~ . y ~'0 :~
, ~. o I ~1 1 ~ ~ z . ~ ~ ~-- ~ I I I I /
.,!; O Z . 5 // \ ~1 I /~ ~
c~ o m o -- -. . r~ Z ~1) 1 ¦ ¦ \ /
~ \\ / I ~ /=
a) ~ // \ / ~ ~ 4=0 c) 1~ I z--~ ~ I I m ~ ~ // ~
r- ~ P~ ) =0 = Z -- C ) I ~ 111 O ~ I \ / ~ / \ Z
~' ~ / \ // ~d Z ~ =orl Z \ /D~
U~ 2i 3 ~ ~) // \ / ~ a~ C) I I \
~ 0 ~ O ~ Z~n .~ ~ U) O O. 1 11 1 0 ; \\ / \ // O
~ ~ o ~ ~a Z

O

.~

:

~:: ~ ~d ~:
~r r~ C a) O
r ~d ~)o o o o o o o o O d O ~ (q ~d r O rl ~ ~) ~ m ~ ri ~> r-l ai ~< ~ rl O
~d ~ ~ c~o o o o o o o o rl O~ N ~ ~ ~\J
r~ o ~ rl ~
r~ ~ ~ O O Ot~ O
u~ O S~ ~u~
do o o o o o o o ~1 0 ~ rl ~, ~, a r-l O E--r-l ~d ~d a) 5~
~ ~ 0 rl ~ ~ _ rl r ;
~d h O
~ ~ r-l r-l ~1 O O O O
c) ~ ¢ m c~ ~
r ~
~L) ~, . ~ ., ' I . ~
` Z ~ ~ O ~) :
~; O ~ o N r-l I
~ ~ ~ m ~ I ~ t/;\ z t~ ~ ~ o ,~ a) ~ = Z ~ / / \\ 11 '' ~ O--Z =~ ~ z // \ ~1) \ ~ r-l \ /5~ 1 rl O tl) \ Z O ~ ~ ~
¢ ~ 9-- V) \ O ~ O t~ r-l ~ 0 \ ~ \ O h \\ /
. ~ z Z I (n I a~
I I

. 31-, d ' 73~

~. ~
~_, ~ ~C
r l O O O O O O O O O O O O
O ~
C' ~0 =t (~1~ (~ N ~D N ~D N ~D N ~D :

~1 ~rl O LS~ O O ~ Lr~ ~ N C~ O O
U~ r~ 1~ (~)~D (Y r~ N N ~D N =t L~
,_ .... ....
r-l O O O O O O O r~ ~I r~

~a ~
O

`- j ~ ~ ~ o ~ ~ ~ o ~ cC ~ O
N ~ O c :

~ ~ `~`
:
': Z Z
.. CD O CD

O O C~ ~ ~ o = O

.~ ~ z _ Z 0 0 I a~ ~3 ~' ~1 M I ~ O-- Z ~ O (~1 ~ I \ / O
h ~ ~ y ~ z \ CD~

o//\l ~:' ~/ //\
. ~ ~ 1~
I I I

'~ O \\~/
. j ~D .:
'.~
'.., ::

: , :

.` . .. . ~ , 3~3 ; C~

F o o o oo o o O ,bD p, ~ m ~ a)~ a) o rl o o u~
E~ rl rl r~l r~I ~1 (~) rl ~r~ (1) ~r ~-r rl O ~I O O ~J r~ O rl ~ O
~:1 O O O O~1 r-l ri rl r S
c~
SI
(I~
a Z >~
~ U~
J~ a~ s~
S~ S~ rl C~
h '`~ a c~ O
~ r~
m ~
a) o ~ o o ~ C) I m ~ bD ~ ;
. ~ ~Do v) r1 r;
~' i ~ O CC 1~ ~ rl,~
rl 0/ ~0 r I li I ~
. . ~ F U~ --~ ~ Z br,~ ~ ~ ~ ' C~ Z
-~ ~ ~ I I \ O ~ 0--0 r~
~ ~) Z ~ ~ O ~ X r~
~

. D ~ <_) ~ // O ~ 0 ~3 a) ' . \\3/ 0-~0 C-~-r~rl td ~ ~1 ~ O:> ~ ~ ::
a) o m o ~
~' X r~~ o .. ~ ~ ~~ U~

.

': :.
.
.. ..

3~

// ~
'>< I
Cl 0=0 C~
C.) ~ I I I
d' ~=0 1 0 = ~O = O
I
I / X
o=o~ I I ,r~
"' (_) -- Z -- C~ --O 1~

X
',; I ~ // :
~ :
`: .

::

.' : -34 -:. . .
.
, ~
. . .. ...
.. . . . .. ... . .

~'7 ~: J I - -- 'I
C~ r _ ~

_ Z C~ ~_ O ~, ~"
\\ ~/ I
L~
1. , I ' ' _ . ~
~ ~ 1 ~,.
. ,, _ , ~

:` f C . I + Z

=0 1~

` ~

r ~.
,^! .
' .

" '; ~j ' '' :': ' a) c, ': :

-35- ;
~;~

-;, .:, , , ~.

.. :, : ., :~

Example 3: Evaluation of the covalent mordanting of ; amine dyes The covalent mordanting of amine dyes with mordants within the scope of the present invention was evaluated according to the following procedure: ~;
Dye-receiving elements were prepared by coating a -poly(ethylene terephthalate) film support with a layer containing gelatin at 200 mg/ft2 t2.16 g/m2)~ a bis(vinyl-sulfonylmethyl)ether hardener at 4.0 mg/ft2 (0.04 g/m2) and a mordant (see Table 3) coated at 0.51 mmoles 03~ reactive site/ft2 (weight ~uantities in Table 2).
Dried samples of each receiving element were laminated to samples of a multicolor image-transfer element , with a viscous alkaline activator comprising 1~2 N potassium hydroxide solution (no developer) spread between. After 10 minutes, the elements were separated and the receiver samples were water-washed for 20 minutes and dried.
The multicolor image-transfer element employed is . represented by the following schematic structure (coverages 20 in mg/ft2; g/m2) .;
.,`~'' ~'~

, ; .

' ~ ~`' ' ,, .

'.
~;
.
:; ' -,. :
.:
.`: :, '' . ' ', , .. . ~:
: - . , . ~: ,: ,. ,;

.. : . ::
:: : : , .'73~

elatin (91~ 0.98) _ ;
blue-sensitive silver halide ~100 Ag; 1.08 Ag);
gelatin (300; 3.24); yellow-dye releaser (58;
0.63); electron donor:
O=C-OCH2CH2NHSO2CH~
N-CHa ~ ~ ~ \O' C ~/ \C/O
CHaN-CH2CH2SO2NHC10H3 7 (73, o.78)~ diethYl lauramide (131; 1.4) gelatin ~1 0; 1.9 ); interlayer scavenger; filter dYe green-sensitive silver halidë (100 Ag; 1.08Ag);
! 10 gelatin (300; 3.24); magenta-dye releaser (67;
0.72); electron donor:

C-N-CH2CH2SOzNHC1sH37 /N \ C H 3 C-o , CH3-N-CH2CH2SO2NHC1sHa7 ~;
, ~; (1.47; 1.59); 2j4-di-n-amylphenol (214; 2.31) ~elatin (120; 1.30)- interlayer scavenger red-sensitive silver halide (lOO Ag; I.O~ Ag);
gelatin t300; 3.24); cyan-dye releaser (41;
0.44); electron donor: -`~ O CH
~. 11 1 : , C-N-CN2CH2SO2NHC1sHa7 CH3-N-CH2CH2SO2NHC1sH37 . - :
.02) 2 4-di-n-amylphenol (135- 1.46) ~ / / / p ~ ene terephthalate) support/ / / /
.~ ' ' The coated samples and results are recorded ..
; in Table 3.

-:. ~;;' m a~ ~o o o co o ~ ~ t~ D ~ CO O O~ ~ 0 _, r~ CO O~ CO cr~ o~ o a~
~: ~
v ~: ~c--o o =~ ~ o co co u~ o ax~ ~ ~ o~ ~ ~ ~co ~co u~ ~ ~ a~ ~ ~ ~ ~ o~ o ~:. . . . . . . . . . . . . . .. . . .
c~ ~o o ~ o o o o o o o o o o o oo o o ~ m _ ,~ ~:n O O u~ ~ O O O~ ~ O
-- ~ ~ CO ~ co co ~ t--P
rl ~
rl O ~ ~.
M m ~ ~
~ a) ooou~r-~oo~ ~ ~ L~ o o o~oo a) ~ a) ~> ~ o ~ o o ~ ~ co ~co ~D ~ ~ O O ~ ~ O
~: ~0 h .......... . . . . . ...
~' ~) ~ ~~1 ~1 ~1 ~1 ~1 ~1 ~1 0 0 0 0 ~1 0 0 0 ~1 ~1 0 ' ' g ~ ~ ~ `"~:
o _~ m C)C>O O N C~O ~t CO O O C~ D ~ O O ~ O
rl ~ 0~ ~ ~CO 0~ O O 0~ C~0~0~ a~ O CO CO
~; ~ a) ~æ
. ~ O ~
~: ~ ~::
. E~ 0~ a~ :.
r-l ::~ O O ~0 0~ ~ Nl ~ O CO ~0 15~ ~ O ~ ~ O ~ O
r-l r-l N ~1 N O CO O N 0~ C~ ~I N N (Y- a~ CO N N O
~ m .......... . . . . . ...
~ ~ ~I r~ r~ r-l O r~ l O O ~I r-l rl O O O ~I r-l O
rrl ~ a)rl rl rl rl r1 rl rl ~ C) rl rl rl rl C) C) rl rl C~
:. ~ bL ~ r1rl ~ r1 rl ~ rl ~, ~ ~ ~ O O O O O O O ~ O O O O ~ ~ 0 0~ " -r~ ~ ~ rl rl rl rl rl rl rl O O rl rl rlrl O O rl rl O ::
P h ~ ~ ~ ~ ~ J~ ~ ~ rl rl ~ ~ ~~ rl rl ~ ~ r1 ;~ ~1 O C) td ~ t~ td td O O ~ O .~

~) O O O O O O O rl rl rl r1 rl rl a~ ~1 O ::
~ ~ ~ e, I e, I e. I e. I ~ I e. ~ ~ ~
~ rl ~ r-l r1 r~ r-l r~ r-l r-l r~ ~ r-l ~ rl ~d r-l ~ rl ~I r-l ~ rl rl ~
d ~ ~ ~ ~ r~ ~ r~ ~r~ r~ ~ r~ P~ r-1 e. ~ e ~ C~ rl U~ M U~ e. ~ ~ ~ e. :~ e. ~ e. ~
r-l r~ r-l r~ r~ r-l r~ ~1 ~1 rl O O rl rl rl ~
., . 01 ',.
_~ ~
~ ~ r-l O ~) ~ ~ O O ~ ~ ~ ~ (~ cc> ~) o ~ 3 ~I
_ ~ ~O O (r~ r~ \1 N ~ r-l ~ ~ ~ ~ ~1 Ll\ r~
. r~ ~1 ~ C~l r~ O r1 ~ C\l ~ (\I \~ ~ l r~
. r :, ,:

Z ~ Ha ~ z c~oP.~
O O ~:
'., V V

~ O O ~ ~", h h rl ~ ~ r~ O C--CO a~ O r~ ~1 fr) ~t IS~
C) O O r~ r~ r~ r 1 r 1 rl r~ -,.. , ~
,, . ~ a:~ , "

:
-, :
:
~ -38-.,. ~
., .
, . . , . . .. , . , .~ .. .. ..... .. .
, . , , ` ~ `
, . ` ' .
. . . . ....
. . .: : , .. . - ~ . . ....... :
., ~. . ..... -.. .
s : :

Table 3 footnotes:
_ a) The percent of covalent bonding was estimated from the dye density loss after treatment of the dyed receiver for 2 minutes with an organic solvent mixture comprising 200 ml MeOH, 200 ml CH2C12, 20 ml H2O and 10 g NHIISCN.
b) A transmission density of 0.9 is approximately equal to : a reflection density of 2Ø
c) Yellow amine dye CH

HN(cH2)2Nso2-9\ /o-N=N a y ;;~

re~.eased from yel.low dye releaser:

SO NHCH CH NCH
~ : l 2 2 21 5 ~

'h N=N S~ ~/ SO C H

aryl C H

~ '^
. ','.
d) Magenta amine dye "'':

HN\ \o-CH NHSO2-~ -N=N- aryl . ~.
, ~

: ~39~ :

, . .

3~

released from magenta dye releaser:

aryl 3 ~ :.
~\
NO

SO NHCH -o\ \N-C-I~ ~-SO2C12H25 ~, SO C H

~` .

e) Cyan amine dye CH CH
HN(CHz)2NS02 \ _ S 2 N H- a~
. aryl-N=N~ OH

; released from cyan dye releaser:
` OH

. ~t' '~ :
; ~ ¦ N=N- aryl 0--3~
o\ /o-SO2NH O ~ ~ 2 1 2 25 '; S02N-CH2CH2NC-~ ~D

.. ,~` ~

~4-i~

.
:
. . : . ::
: .

3~ :

f') Mo~dants:
~CH -CH) - CH -CH-~ ~
Control l~ Cl~

CHS N CH
CH

~C~12 C~I ~ CH2-CH ~ CH2-CH~ ' Control 2:

CH2 ~CH-CH2t CH -N-CH
~H

-CH2-CH - - ----CH2-CH _ :.
A L CH N(C ) ~ H SCH C

F ;~ ` F
B ~e ~.~ 11 )~
~(CH ) 3¦ L CHZSCH=CH~ CH CH

. .
.
~41- :

..

..

J3~

.--CH -CH--C ; /1~ ~CH COO
~ CH -CH -SO CH=CH 3 C H

F /N\ ----C H 2 ~ C H - .
D: ~ N ~ ~ I S O ~ ~ .
\H CH2SO CH2CH2C I

: ~:
' .
FC H -C H~FC H - CH ~ ~;

L _I L C H S O C H C H C I

~o 20 ~ ~

;--CH -CH~ \ ~ ~
~,1 o . Na + ~k 1l ; ~
l CH SCH CH C I
; (C~12) 3S03 30 _ o _ . ~:
.` ~o i, .

: . :
~; , :
~,` ` ' ,' _L~2_ ,'',' 3~

CH _ _ G I-CH -C ~ ~ CH -CH - -I CH S0 CH CH Cl ~ L (CH~ L ~2~2 ~o -CH -CHr - -CH -CH -2~l\2~1, ~: `

H: CH N(CH ) Cl ~

:' `

~CH -~ CH -C - ¦

L cH2N-CH CI (CH2)2 3 . NHCNHCCH CH Cl : 1 o o 1 . ;~
' ~ CH ~ t~ :
~ ~ 3 (C112~ 2 CH-CH
.~ CH N-CH . NHCNHCCH CH Cl _ _ 2 ' C~ o 0 9 :~

', : :

` 3 : :
` ' ~

;: ~

3~3 -CH -CH - - -CH -C
K: 2 1 2 1 C=O C=O
. NH NH
ao (CH ) NHCNHCCH CH Gl ::
~11 0 _ :20 ' ~

-CH2-CH -- _ __ -CH2-CH -L: C=0 Na ~ ~ :

(CH2)3S03 HNCNHCCH2CH
. ;~ ~

~CH -CH ~ f H~-C

,~ NH Na 0 CH -C-CH (CH 2 ) 2 `
CH S0 NHCNHCCH CH Cl 3 1 11 11 2 2 :
. :.
:. _ _ _ CH -CH

. CH N(CH3) =

` 1 1 ;~, , : . .-4L~ _ .
`:

CI~ CH~-: P F ~ I ~CH -C
C=O Na C=O i.
; NH O O
. CH -C-CH CH CH NHCCH CH Cl :~
:. 3 1 3 2 2 2 2 '~
` CH2SO3 1 _ _ 1 '' ' ~ .

~:;., E;xample 4: Evaluation of' the covalent mordanting of -sulfonamide dyes : ;~
.j , , .` Samples of the receiver elements described in ~; .

.! Example 3 were laminated to samples of fogged (developable) - ;
~ photosensitive elements comprising a poly(ethylene terephalate~
!: ~
support having coated thereon a layer containing a negative~
working silver bromide emulsion at 0.3 g. Ag/m2, gelatin at ;~:

.~i 10 3.3 g/m2 and either the cyan-dye releaser I at 0.3 mmoles/m2, rnag,enta-dye releaser II at 0.3 mmoles/rn2, yellow-dye releaser ,~
, III at 0.6 mmoles/m2 or yellow~dye releaser IV at o.6 mmoles/m2.
'~ A pod containing a portion of' a viscous processing composition comprising 48 g KOH, 7.2 g of 4-hydroxymethyl-4-methyl-l-phenyl-3-pyrazolidone and 40 g of carboxymethyl .
1 cellulose per liter of water was spread between the laminated :
_ . ;

` ' '', ` ~ , '7~

st:rllcture to provide a 0.056mm-thick developer layer. After 5 minutes, the elements were separated and the dyed receivers : ;
were washed in water for 20 minutes and air dried.
The percentage of covalent bonding was then esti-mated by treatment in an organic solvent mixture as described ; ~ .
in Example 3. ;
The results are recorded in Table 4. ~ :

Y~

,~
-; ,:
' . :
. -46- :
.

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

3~
c ) ¦ o o r~ ~ co co r~ O O cr~ o t_ o o o o o o a~ rl~ J ~ N
`
a) o a~o ~co~ Lr~O o ~ ~ ~ o o OCO~D O
O O CO ~ ~D O O O L~ O
S~
r ~ r I rl ~1 ~1 ~I r~ Or I r~ ~I r~ O
m {~
, m ~ C~ O O ~ ~ C~ O O O ~ ~ C~ O O O O O O
t~ ~ L~ r ~ J r l a~ ~^ ~ : ::
rl ~ c>
~ ~ a) a~ ~:
rl O ~0 >~ a) ;r~ o ~t r~ o o o L~ o o o c~ r~ O
u~ m ~d ~ ~ o r1 ~1 o ) ~o tY~ ~ o o o t_ o o o o If ~ =t O
s ~ ~ ......... . . . . . .... ~., ~ r~ r~ r~ r~ r~ r~ O ~1 0 rJ r~ r~ I
' ~ ..
~ r~ ~t o ~3 m rl ~ Q) ~ O O (Yl~) O ~ r-l o o o a~ ~ o o o o o o O 1~ t~ ~r) ~ r J r I c~ ~ r~
rl ~
O O `- ~ c;:) ~0 ~ 00 ~ ~0 0 ~ Lf~ ~D O O OOC) t--O '`~: H H ~ a~o~ o c~a:~ oo H o o c~ o c~ o o o ci~ ~ o ~:
~d ~ ~ H ~ ......... . . . . . .... .~
s~ ~ a) ~ o o ~ o o o o o ~i o o o ::
c) F~ ~ ol oo~oo~oo ~ ~1 o o o oooo ~ .,.
o~ a~ ~ a~co~ o ~o o ~ o co O O OoO ~ O
~1 :~ Lr~a~oo ~ ~ ~ o o o~o ......... . . . . . ....
(L) Q 0000000 0 0 0 00 ,.
." : ., , ~ ~ ~ O O O O O O O ~ ~ O O O O ~ ~ O O ~ ' .' ' ~; ~ ~ ~1 rl rl rl rl ~ rl O O rl rl rl rl O O ~rl rl O .
H O C~ ~d ~d ~d ~d ~d O O $~ $~ ~d ~d ~d O $~ ~ ~d ~d ~ ~ C~ c~ C) C~ C~ $~ $~ td ~d c~ C~ c> $~ ~d ~d c~ c) td : ! $~ $~ ~ ~ $~
O O O O O O O rlrl rl rl rl r~ a~ a~ a) ~1 ~1 ~1~1~1~ ~I ~d ~ ~d ~I ~d ~I ~d ~I ~d ~I ~d ,1 rl rl rd ~ ~ u~ rn tn ~n rn rn tQ ~ d t~d td . r.
~1 ~ ~ ~ ~ ~ ~ ~ d F~ d ~ td o t.~) t/~ a) a) ~ ~ ~ ~ ~ :~, ~ P c~ ~ c~ ~ c~ c~ ,0 c~ ,~ c~
,~--' ~ $1 $~, $~, $ I ,r~; $ ' ~r,, ~r,; ~;: $~ ~1 $ I rd ~ ~ ~r.) $ ~ ~) $ ~ $ ~ $-l $~
.; Ir; O o ~ 1 rl rl r-l rl ~d ~d ~ d td td C) C~ C~
~,: ~ $~ C~ C) C) C) C) C~ ~d rd ~d ; tU
:: ~ r~ O ~) r--t\l o o ~ tr) r.~ tY~ o ~:) O ~ r-l 15\ t\J ~ ~ r~ rl t\~ r~
\ rl t\) r.~J t~J rl (\~ ~ rl tY~ r.
.~ ~ I
'~ ~d Ei `
.~ ~ rl ~
~.~ O h rl rl '' ~ a) o o :~' $~ $~ ~ H m 17 ~ ~1 ~3 J~
~; $~
Z O O

rl rl $~ O O
a~ ~ $~ ,~
~ J~
rl ~ ~ r 1 (~I ~) 3 L~ t)~ o ,~ t\) ~ ~ L~
a o o r-l rl rl r-l rl r-l rl C) C~ C~
a~ --~;
m .
.~ ` ,~ . i Sulfonamide dyes:
a) yellow dye ~-o~
o\ ~-N---N
o=~ CONHCH3 \ _ / 2 2 released from IV: ~-OH
~ G--a~ "
~ ~C O N ~1 ( CH 2 ) 4 o_ ~ ' C 5 H 1 1 C H -t 111 5 1 1 -- : ~

/~ O
\ ~ CNHCH
=N
N=N-b) yellow dye o~ N---N
o~ -CN
OCH

N=N-3~ ~5 SO2NH2 6~ = 9 1 : ~

'; ' ~
.~ ' .

.. , . :, , :

released from III: ~:

0 ~1 :

~CONH ( CH2) 4~ / 5 1 1 N H S O - e~

2 \ _ / 3 N=N

H O- ~ - C N
/N---~
C~H5 .

c ) magenta dye OH

- S 2 N H C ( C H

CH3SO2NH N=N-~ ~-SO~NH2 released from II:

OH
(CH ) o~ -C 11 -t CH
~ ~- - 0;~ 1 3 , 2 \~ 2 :~
N NH

_1~9_ , 3 ~

d) cyan dye OH

~ ~ a - S O N l l N- N~ / o - N O z 50 NHz released from I:

OH ~_~
C O N H ( C H ) O--~ --C H --t C 5 H - t - t NHSO --O
2 \~= ~
S O 2 N H N= N~ ~ N 2 `8' ~ so CH ~ `
:: ~o~
OH

:~ Example 5: Evaluation of covalent mordanting of phenol . ~ dyes Samples of the receiver elements described in ~; Example 3 were laminated to samples of single-layer, photosensitive image-transfer elements containing quinone dye releasers of the type described by Chasman et al, U.S.
`~ Patent No. 4,139,379 issued February 13, 1979. Each element consisted of a poly(ethylene terephthalate) fllm support having coated thereon a layer containing a negative-working silver halide emulsion at 100 mg Ag/ft2 (1.08 g/m2), : gelatin at 200 mg/ft2 (2.16 g/m2), a ballasted electron-accepting nucleophilic displacement (BEND) compound as the `

.' : ~' `

dye providing substance, and an electron donor. The BEND
compound and electron donor were dissolved in an equal weight of diethyl lauramide and dispersed in gelatin prior to coating.

Dye-Providing Elemenks BEND Compound Electron Donor Coating No. No. moles/ft2 No. moles/ft 1 1 5 x 10-5 1 1.0 x 10-4 2 2 3.5 x 10-5 2 7.0 x 10-5 The phenol dyes released from the quinone BEND
` compounds were transferred to the receiver elements by employing the procedure described in Example 3.
The percentage of covalent bonding was then estimated by treatment in an organic solvent mixture as described in Example 3.
The results are recorded in Table 5.
i`` , ~
, ::

:

:~ :

; ml O O ~nco ~ O~ o m I ~
. . V ~ ,.
r ,~
~ ~ ~ ~ a)~ o o~ ~--~ r l r~ ~ O
o 5: r C~~ ~ H O ~\1 tr)J ~ O O
~ ~ r : ~1 rl H H H O H H
U~ ~ ~
,; ~ O C~ ¦ O O OC Ll~ O ~ O O
~ ~ ~ ~.
? ~ a) S ~~2 a) ~ ~
H r I H O r-l O Ln O O ~ O
, ~ ~1, ~1 1~:) ~ ~ O \D ~--O
o ~ m ...... ..
`` ~> ~ ~o o o o o o o ~,~.. ..
~`; :

'i ~ ~ o o o. o o o o ~ rl ~ ~ ~ ~ ~ O , .
, ! O .~ ~ ~ ~ ~ ~C ~ ~ rl ~ O ~
. ~

~ o o o ~ a~
a) ~ ~ ~ ~
H _ ~ ~ rl r~ r-l rl td rl rl ,0 td ~ J~ ~ ~r~
d ~ c~ r~ tn rn ~n ~ :~ td td ~
E I ~I td U~ rl rl ~I ~d ~ r~ r1 `: :-'~ o a~ O a) p~ , O O ~ rl rl td C~ C
C) td ~d t~ :'~
, . ~ ~t r-l O (r) t--O ~ ~t ~
. ~. ~ ~{) O ~ rl c~l t~ H r1 . ~ ~ bD r~ r l ....
td . h r-l N
:~ O rl r~

z ~ ~ ~ m ... ~
` rl r-l :, ~ O O `.
r~ rl rl r~
., a) o o ~, :: `
m -~:
~,`-, ~ ~. .

-52- :~

.: ` ; `, ~ ,; ~, ;
: - -. ~ . ., ` . . ~ ` . ` ; - ~

Phenol dyes:
a) yellow dye H O ~ - N H S O ~ - N= N- 3 ~

.' ' .
; released from B~ND Compound 1:
, . I

~.
~ O
R~ ~-~ /C1 2H25 : R R
` C H ~ R
O
' \ /- :' C H ~
R = - C H 2 N C O- ~ - N H S 2 - ~ - N= N - ~\ I

; 3 `~`'' ;
.
~: b) cyan dye ~;
. : ,.
`~` NOz ~ ~ OH N=N-~ ~3-OH

;:~ released from BEND Compound II:
':' O ` ~;
`- C 3 H 7 ~ ~ R
o fi R R C. 6 3 ~.

~53-3~

CH NHCH :
R = -CH NCO --~ ~D I 3 ~:
NHSO OzS \ _ / :
~ N=N-o~ ~-OH

O N
, ~, , ": ., Electron Donor l .
IC H 3 ' ~ ~
C9NCHzCH2NHS02CH3 : `
N~CH3 O
~ C~ O : .:
O=C : ..
CH NCH CH SO NHC H
5 Z :2 2 1 8 37 . '"' :~
Electron Donor 2 . CH
~\ /N

O=C O
Y I ' ~:
N\ ~ ;:
\N/ SOzNHC1~H2s ' O=C~
S02NHClzH2s ~- .

. : .
~5~

, ~

~'73~

; The invention has been described in detail with ~par-t:icular reference to cer-tain preferred embodiments thereo~, but it will be understood that variations and modi~ications can be e~ected within the spirit and scope of the invention.

' ' SUPPLEMENTARY DISCLOSURE
The following additional examples further illustrate the present invention. (Preparation 1 is disclosed in page 25, lines 9-21 of the Principal Disclosure).

Preparation 2 Part A - Preparation of N-(3-Methacrylamidopropyl)-N'-(3-chloropropionyl)urea Pyridine (7.9 g~ 0.1 mole) was added dropwise to a mixture of ~-chloropropionylisocyanate (13.3 g, 0.1 mole) and N-(3-aminopropyl)methacrylamide hydrochloride (1708 g~
0.1 mole) in N,N--dimethylformamide (80 ml) at 0C. The mixture was left to stlr o~ernight at ambient temperature.

This mixture was then poured onto ice, and the product filtered. Recrystallization ~rom absolute e~hanol (400 ml) ~-~
gave l-(3-chloropropionyl)-3-methacrylamidopropyl urea, mp 131~2C.
Yield = 70 percent.

Anal- Calcd- for CllH18ClN303: C, 47.9; H, 6-6; Cl, 12-93 N, 15-2-Found: C, 47.1; H, 6.7; Cl, 13.0; N, 20.6. ~-Mass Spectrum m/e (M+, 275).

Part B - Poly[acrylamide-co-N-(3-methacrylamidopropyl)-N'-(3-chloropropionyl)urea] (8:2 w) A solution Or 36 g o~ acrylamide, 9 g of N (3-methacrylamidopropyl)-N'-(3-chloropropionyl)urea, and 225 mg of 2,21-azobis(2-methylpropionitrile) in 405 ml of dimethyl-sulfoxide was flushed with nitrogen for 1/2 hour and heated ;

at 60C overnight to yield a viscous polymer solution. The polymer was isolated by precipitation from acetone, and it was collected by ~iltratlon and dried in vacuo at room temperature to give 45 g.
[~]0 1 NNaCl = 1-35-::

Preparation 3 Part A - Preparatlon of N-(2-(Methacryloyloxyethyl)-3-chloroproplonamide Pyridine (15.8 g, 0.2 mole) was added dropwise to a mixture of 3 chloropropionyl chloride (12.7 g, 0.1 mole) and 2-aminoethyl methacrylate hydrochloride (16.5 g, 0.1 mole) in N,N-dimethylform~mide (20 ml) at 0C. The mixture was le~t to stir overnight at ambient temperature. The solvent was evaporated in vacuo, and the residue was dis-solved in dichloromethane (500 ml). The mixture was then washed with satur ted sodium chloride (249200 ml), dried over anhydrous magnesium sulfate, and the solvent removed.
The product was collected by distillation, bp 104-110C at 2~.
Yleld = 55 percent.

Anal. Calcd. for CgH14ClNO3: C, 49.2; H, 6.4; Cl, 16.1, N, 6.4.
Found: C, 49.1; H, 6.8; Cl, 16.4; N, 6.8.

Part B - Poly[vinylbenzyltrimethylammonium chloride-co-N-(2-methacryloyloxyethyl)-3-chloropropionamide]
(1:1 w) A solution of 5 g of vinylbenzyltrimethyl a~nonium chloride, 5 g of N-(2-methacryloyloxyethyl)-3-chloropropionamide, and 50 mg of 2,2'-azobis(2-methylpropionitrile) in 50 ml of dimethyl sulfoxlde was flushed with nitrogen for 1/2 hour and then heated at 60C overni~ht. The resultant polymer was isolated in acetone, collected by ~iltration, and dried in vacuo at room temperature to yield 9.4 g.
Anal. Found: C, 54.4; H, 7.8; Cl, 13.4; N, 6.o.

[n]o. lNNaCl = 0-81-Preparation 4 Preparation o~ 2-Chloroethylsulflnylmethylstyrene Vinylbenzyl 2-hydroxyethyl sulride is oxidized with a 6.5 percent molar excess of sodium meta-periodate (NaIO4) in a 1:1 (volume) mixture of water and methanol at .~,.. s~.,; .

t~3 ~ ~

. 0C over a 3-hour period to 2-hydroxyethylsul~inylmethyl-styrene. The precipitated sod~um lodate (NaI03) is removed by filtration and the filtrate extracted with methylene chloride. The extracts are dried over MgS04 and the solvent removed to provide the crude intermediate, which is crystallized -~
; rrom l:lv hex~ne:ethyl acetate.
The intermediate is converted to the 2-chloroethyl-~ulfinylmethylstyrene by treatement with thionyl chloride in tetrahydrofuran.
:' :

~: CH2=CH CH2=CH

CH2SCH2C 2 CH2$-CH2CH2 ' :' ~, ~H2=CH

~ ~I socl2_ `
; CH2S~CH2CH2Cl tetrahydrofuran : Preparation 5 Preparation of 2-(2-Chloroethylsulfonylamino)-.~ ethyl methacrylate 2-Aminoethyl methacrylate hydrochloride is condensed with 2-chloroethanesulfonyl chloride to produce the 2-(2-chloroethylsul~onylamino)ethyl methacrylate.

! ` ~

. 3 ,CH3 . 2 , + ClS02CH2CH2Cl ~ CH2 , '~ C=O C=O

OCH2CH2NH2 HCl OCH2CH2NHS02CH2CH2Cl .

7 ~ `' .` 1_ ;..

3~

Preparation 6 Preparation of Vinylbenzyl 3-chloropropionate Vinylbenzyl alcohol is condensed with 3-chloropropionyl chloride by conventional esterification procedures to produce the vinylbenzyl 3-chloropropionate.

~, O
~ ClccH2CH2cl ~ R ~ o .
Preparation 7 Preparation of 6-Acrylamido-6-methyl-3-oxoheptyl chloride The title compound is prepared by the Ritter reaction of acrylonitrile with 7-chloro-2-methyl-5-oxo-1-heptene in the presence o~ sulfuric acid. ;
CH O
3 " H SOI
CH2=CH-CN + CH2=C-CH2CH2CCH2CH2C1 2 ~ CH2=CH
C=O '' NH

CH3-C_CH3 CH2CH2CCH2cH2cl ~ , O ~.

Preparation 8 Monomer of Vinylbenzyl 2-chloroethylsulfone To a solution of 50 g (.221 moles) of vinylbenzyl 2-hydroxyethyl sulfone, 19.2 g (.243 moles) of pyridine, and 1 g of _-dinitrobenzene in 500 ml o~ tetrahydrofuran at O to . . .,:
~C was added dropwise 28.9 g ~.243 moles) of thionyl chloride.
After the addition was complete, the mixture was refluxed for 2 hours, cooled to O to 5C, and the pyridine hydrochloride ~;
was removed by filtration. The solvent was then evaporated to leave an oil which was added to 1 1 of ice water to .

"
, ~"' ' ~ ~ ' ~ "
3~

crystallize the product, me solid was collected by ~lltra~
tion and recrystalllzed from 1.6 1 o~ 50 percent water, 50 percent ethanol to give 46 g (85~2 percent) of the desired product (mp 62 to 84.C).

Preparation 9 Poly(vinylbenzyl 2-chloroethyl sulfone) A solution of 35 g of ~vinylbenzyl 2-chloroethyl sulfone as in Preparation 3 and 175 g of 2g2'-azobis(2-methyl-propionltrlle) in 70 ml o~ dlmethyl sul~oxlde was heated at 60C under a nitrogen atmosphere for 25 hours. The polymer Ic was precipitated in methanol, collected by ~iltration, and : dried in vacuo at room temperature to glve 32.5 g (93 percent) of polymer.
{n} D~F = 0.65.

Anal. Calcd. for CllH13C102S: C~ 54.0; H, 5.3; Cl, 14.5, S, 13.1.
Found: C~ 54.1; H, 5.6; Cl, 13.9; S, 13.1.
All inherent vlscosities reportecl herein are determined at 25C at 0.25 g/deciliter of solutionO

A copolymer derived from vinylbenzyl~2-chloroethyl .sulfone is described ln Preparation 1 (see page 25 of the Principal Disclosure).

~ I

:

Claims (52)

It is claimed:

1. A photographic element comprising a support, a nucleophilic photographically useful and/or active fragment having appended thereto a moiety selected from the group consisting of ZNHR, -SO2NHR and wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with the NH to complete an N
containing heterocyclic group; and a polymeric mordant, said polymer comprising recurring units having the formulas selected from the group consisting of:
A) and B) wherein R2 is H or alkyl;
R1 is H, alkyl or aryl;
L is a linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3 wherein R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
W is an electron-withdrawing group selected from the group consisting of SO2, CO,, SO, and ;

m is 1 or 2;
n is 0 or 1;
with the proviso that when n is 0, W is S02 or ?
OC; and X is a leaving group which can be displaced by nucleophiles or eliminated in the form of HX by treatment with base, said photographically useful and/or active fragment and said recurring units forming a covalent bond on contact.

2. The photographic element of claim 1 wherein the photographically useful and/or active fragment is selected from the group consisting of dyes, dye precursors, development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, couplers, developing agents, silver halide solvents, silver complexing agents, toners, hardeners, fogging agents, antifoggants, chemical spectral sensitizers and desensitizers.

3. The photographic element of claim 1 also comprising a photosensitive silver halide emulsion.

4. The photographic element of claim 1 wherein the polymer is a cationic polymer.

5. The photographic element of claim 1 wherein the polymer is an anionic polymer.

6. The photographic element of claim 1 wherein the polymer is a nonionic polymer.

7. The photographic element of claim 1 wherein said polymer contains recurring units having the formula selected from the group consisting of:

and said photographically useful and/or active fragment having appended thereto ZNHR wherein the polymeric mordant is anionic and said moiety being ZNHR, -SO2NR or when the polymeric mordant is cationic or nonionic.

8. The photographic element of claim 1 wherein said polymer containing recurring units has the formula selected from the group consisting of and wherein said photographically useful and/or active fragment has appended thereto ZNHR when the polymeric mordant is cationic or nonionic and said moiety being ZNHR, -SO2NHR or when the polymeric mordant is cationic.

9. The photographic element of claim 1 wherein said polymer is cationic and contains recurring units having the formula selected from the group consisting of and said photographically useful and/or active fragment having appended thereto ZNHR.

10. The photographic element of claim 1 wherein the polymer is a copolymer containing units of vinylbenzyl-trimethylammonium chloride.

11. A photographic element comprising a support, a dye or dye precursor having appended thereto a moiety selected from the group consisting of ZNHR, -S02NHR and wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with NH to complete an N
containing heterocyclic group; and a layer comprising a polymeric mordant, said polymer comprising recurring units having the formula selected from the group consisting of and where R2 is H or alkyl;
R1 is H, alkyl or aryl, L is a bivalant linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;
R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
W is selected from the group consisting of S02, CO, ?
OC ,SO, and ;

m is 1 or 2;
n is 0 or1;
with the proviso that when n is 0, W is S02 or ?
OC; and X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor and said recurring units forming a covalent bond on contact.

12. The photographic element of claim 11 wherein the polymer is a cationic polymer.

13. The photographic element of claim 11 wherein the polymer is an anionic polymer.

14. The photographic element of claim 11 wherein the polymer is a nonionic polymer.

15. The photographic element of claim 11 wherein said polymer contains recurring units having the formula selected from the group consisting of:

and said dye or dye precursor having appended thereto ZNHR
wherein the polymeric mordant is anionic and said moiety being ZNHR, -S02NHR or when the polymeric mordant is cationic or nonionic.

16. The photographic element or claim 11 wherein said polymer containing recurring units has the formula selected from the group consisting of and wherein said dye or dye precursor has appended thereto ZNHR when the polymeric mordant is cationic or nonionic and said moiety being ZNHR, -SO2NHR or when the polymeric mordant is cationic.

17. The photographic element of claim 11 wherein said polymer is cationic and contains recurring units having the formula selected from the group consisting of and , said dye or dye precursor having appended thereto ZNHR.

18. The photographic element of claim 11 wherein the polymer is a copolymer containing units of vinylbenzyl-trimethylammonium chloride.

19. A photographic element comprising a support and a layer containing the reaction product of a) a photo-graphically useful and/or active fragment having appended thereto a moiety selected from the group consisting of ZNHR, -SO2NHR and wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with the NH to complete an N
containing heterocyclic group and b) a polymeric mordant, said polymer selected from the group consisting of and wherein R2 is H or alkyl;
R1 is H, alkyl or aryl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CoNHR3;
R3 is selected from the group consisting of alkylene-arylene and arylenealkylene;
W is an electron withdrawing group selected from the ?
group consisting of S02, CO, OC, SO, and ;

m is 1 or 2;
n is 0 or 1;
with the proviso that when n is 0, W is S02 or ?
OC; and X is a leaving group which can be displaced by nucleo philes or eliminated in the form of HX by treatment with base.

20. The photographic element of claim 19 also comprising a silver halide emulsion containing layer.

21. The photographic element of claim 19 wherein said polymer contains recurring units having the formula selected from the group consisting of:

and said photographically useful and/or active fragment having appended thereto ZNHR wherein the polymeric mordant is anionic and said moiety being ZNHR3 -,S02NIIR or when the polymeric mordant is cationic or nonionic.

22. The photographic element of claim 19 wherein said polymer containing recurring units has the formula selected from the group consisting of and wherein said photographically useful and/or active fragment has appended thereto ZNHR when the polymeric mordant is cationic or nonionic and said moiety being ZNHR, -S02NHR or when the polymeric mordant is cationic.

23. The photographic element of claim 19 wherein said polymer is cationic and contains recurring units having the formula selected from the group consisting of and said photographically useful and/or active fragment having appended thereto ZNHR.

24. The photographic element of claim 19 wherein said photographically usesul and/or active fragment is a dye or dye precursor.

25. The photographic element of claim 20 wherein said photographically useful and/or active fragment is a dye or dye precursor.

26. A photographic film unit comprising a support, a silver halide emulsion, a dye or dye precursor having appended thereto a moiety selected from the group consisting of ZNHR, -SO2NHR and wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with the NH to complete an N
containing heterocyclic group and a layer comprising a polymeric mordant, said polymer comprising recurring units having the formula selected from the group consisting of:

A) and B) wherein R2 is hydrogen or alkyl;
R1 is hydrogen, alkyl or aryl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;

R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
W is an electron--withdrawing group selected from the ?
group consisting Or S02, CO, OC, SO, and;

m is 1 or 2;
n is 0 or 1;
with the proviso that when n is 0, W is S02 or ?
OC; and X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor and said recurring units forming a covalent bond on contact.

27. The photographic film unit of claim 26 wherein the polymer is a cationic polymer.

28. The photographic film unit of claim 26 wherein the layer comprising a polymeric mordant comprises a copolymer comprising from 30 to 70 weight percent of ethylenically unsaturated monomers and from about 70 to 30 weight percent of the units of claim 26.

29. The film unit Or claim 28 wherein the polymer is a cationic polymer.

30. The photographic film unit of claim 26 wherein X is selected from the group consisting of hydroxy, chloro, bromo, iodo, alkyl and arylsulfonyloxy, sulfonyloxy, amino, sulfato and sulfonylfluoride.

31. A photographic film unit comprising a support, a silver halide emulsion, a dye or dye precursor and a layer comprising a polymeric mordant, said polymer containing recurring units having the formula selected from the group consisting of:

and wherein R2 is hydrogen or alkyl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3, R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
R1 is hydrogen, alkyl or aryl;
n is 0 or 1; and X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor having appended thereto ZNHR, wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with NH to complete an N
containing heterocyclic group when the polymeric mordant is anionic and said moiety being ZNHR, -SO2NHR or when the polymeric mordant is cationic or nonionic.

32. A photographic film unit comprising a support, a silver halide emulsion, a dye or dye precursor and a layer comprising a polymeric mordant, said polymer containing recurring units having the formula selected from the group consisting of:

and wherein R2 is hydrogen or alkyl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;
R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
R1 is hydrogen, alkyl or aryl;
X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor having appended thereto ZNHR
wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together to complete an N containing heterocyclic group when the polymeric mordant is cationlc or nonionic and said moiety being ZNHR, -SO2NHR or when the polymeric mordant is cationic.

33. A photographic film unit comprising a support, a silver halide emulsion, a dye or dye precursor and a layer comprising a cationic polymeric mordant, said polymer con-taining recurring units having the formula selected from the group consisting of:

a) and b) , wherein R2 is hydroxy or alkyl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;

R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
R1 is hydrogen, alkyl or aryl;
X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor having appended thereto ZNHR, wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with the NH to complete an N
containing heterocyclic group.

34. The photographic film unit of claim 26 wherein the polymers are copolymers containing units of vinylbenzyl-trimethylammonium chloride.

35. A photographic film unit comprising:
a) a support having thereon at least one photo-sensitive silver halide emulsion layer having associated therewith a dye or dye precursor having appended thereto a moiety selected from the group consisting of ZNHR, -SO2NHR
and wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with the NH to complete an N containing hetero-cyclic group;

said film unit containing a silver halide developing agent and wherein said dye or dye precursor and said recurring units form a covalent bond on contact.

36. The photographic film unit of claim 35 addi-tionally comprising:
d) a neutralizing layer for neutralizing said alkaline processing composition located on a cover sheet superposed over said photo-sensitive silver halide emulsion layer; and e) a timing layer which is permeable by said alkaline processing composition after a predetermined time and is located between said neutralizing layer and said photosen-sitive silver halide emulsion.

37. The photographic film unit of claim 36 wherein:
a) said dye image-receiving layer is located between said support and said silver halide emulsion layer; and b) said cover sheet is transparent and is located over the photosensitive silver halide emulsion layer outermost from said support.

38. The photographic film unit of claim 37 wherein said discharging means is a rupturable container containing said alkaline processing composition and an opacifying agent, said container being so positioned during processing of said film unit that a compressive force applied to said container will effect a discharge of the container's contents between said timing layer and the outermost photosensitive silver halide emulsion layer of said photosensitive element.

39. The photographic film unit of claim 36 com-prising:
a) a photosensitive element comprising a trans-parent support having thereon the following layers in sequence: an image-receiving layer;
an alkaline solution-permeable, light-reflective layer; an alkaline solution-permeable opaque layer; a red-sensitive silver halide emulsion layer having a ballasted redox cyan dye releaser associated therewith; a green-sensitive silver halide emulsion layer having a ballasted redox magenta dye releaser associated therewith; and a blue-sensitive silver halide emulsion layer having a ballasted redox yellow dye releaser associated therewith;
b) a cover sheet superposed over said blue-sensitive silver halide emulsion layer and comprising a transparent support coated in sequence with said neutralizing layer and said timing layers; and c) a rupturable container containing said alka-line processing composition and an opacifying agent, said container being so positioned during processing of said film unit that a compressive force applied to said container will effect a discharge of the container's contents between said timing layer and said blue-sensitive silver halide emulsion layer.

40. The photographic film unit of claim 36 wherein the polymeric mordant is a cationic polymer.

41. The photographic film unit of claim 36 wherein the polymeric mordant is an anionic polymer.

42. The photographic film unit of claim 36 wherein the polymeric mordant is a nonionic polymer.

43. The photographic film unit of claim 36 wherein the image-receiving layer comprises a copolymer comprising from 30 to 70 weight percent of ethylenically unsaturated monomers and from about 70 to 30 weight percent of said recurring units.

44. The photographic film unit of claim 36 wherein X is selected from the group consisting of hydroxy, chloro, bromo, iodo, alkyl and arylsulfonyloxy, sulfonyloxy, amino, sulfate and sulfonylfluoride.

45. The photographic film unit of claim 36 wherein said polymeric recurring units have the formula selected from the group consisting of:

and wherein R2 is hydrogen or alkyl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;

R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
R1 is hydrogen, alkyl or aryl;
n is 0 or 1; and X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor having appended thereto ZNHR, wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together to complete an N containing heterocyclic group when the polymeric mordant is cationic or nonionic and said moiety being ZNHR, -SO2NHR or when the polymeric mordant is cationic or nonionic.

46. The photographic film unit of claim 36 wherein the polymeric recurring units have the formula selected from the group consisting of:

and wherein R2 is hydrogen or alkyl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;
R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
R1 is hydrogen, alkyl or aryl;
X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor having appended thereto ZNHR
wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together to complete an N containing heterocyclic group when the polymeric mordant is cationic or nonionic and said moiety being ZNHR, -SO2NHR or when the polymeric mordant is cationic.

47. The photographic film unit of claim 36 wherein the polymeric recurring units are cationic and have the formula selected from the group consisting of:

a) and b) , said dye or dye precursor having appended thereto ZNHR, wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with the NH to complete an N
containing heterocyclic group.

48. The photographic film unit of claim 36 wherein the polymer contains units of vinylbenzyltrimethylammonium chloride.

49. In a process of producing a photographic transfer image in a photographic element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material, a receiving layer, a barrier associated with a neutralizing layer being permeable by said alkaline processing composition after a predetermined time and which is located between said photosensitive silver halide emulsion layer and said neutralizing layer, comprising:
a) treating said element with an alkaline pro-cessing composition in the presence of a silver halide developing agent to effect development of each of said exposed silver halide emulsion layers, i) an imagewise distribution of dye image-providing material being formed as a function of development and ii) at least a portion of said imagewise distribution of dye image-providing material diffusing to said dye image-receiving layer; and b) neutralizing said alkaline processing compo-sition by means of said neutralizing layer associated with said photographic element after said predetermined time;
the improvement wherein said dye image-providing material has appended thereto a moiety selected from the group con-sisting of ZNHR, -SO2NHR and wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together with the NH to complete an N
containing heterocylic group; and the receiving layer con-tains a polymer containing recurring units having the formula selected from the group consisting of:

A) and B) wherein R2 is hydrogen or alkyl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;

R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
W is an electron-withdrawing group selected from the group consisting of SO2, CO, , , and ;

m is 1 or 2;
n is 1 or 1;
with the proviso that when n is 0, W is SO2 or ; and X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor and said recurring units forming c covalent bond on contact.

50. The process of claim 49 wherein the polymeric recurring units have the formula selected from the group consisting of:

and wherein R2 is hydrogen or alkyl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;

R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;

R1 is hydrogen, alkyl or aryl;
n is 0 or 1; and X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye, dye precursor or dye released from dye-providing material having appended thereto ZNHR, wherein Z is selected from the group consisting of alkylene, arylene-alkylene and cycloalkylene and R is H, alkyl or with Z
can be taken together with NH to complete an N containing heterocyclic group when the polymeric mordant is anionic and said moiety being ZNHR, -SO2NHR or when the polymeric mordant is cationic or nonionic.

51. The process of claim 49 wherein the polymeric recurring units have the formula selected from the group consisting of:

and wherein R2 is hydrogen or alkyl;

L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;
R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
R1 is hydrogen, alkyl or aryl;
X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor having appended thereto ZNHR when Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together to complete an N containing heterocyclic group when the polymeric mordant is cationic or nonionic and said moiety being ZNHR, -SO2NHR and when the polymeric mordant is cationic.

52. The process of claim 49 wherein the polymer is cationic and the polymeric recurring units have the formula selected from the group consisting of:

a) and b) , wherein R2 is hydrogen or alkyl;
R1 is hydrogen, alkyl or aryl;
L is a bivalent linking group selected from the group consisting of alkylene, arylene, arylenealkylene, COOR3 and CONHR3;
R3 is selected from the group consisting of alkylene, arylene and arylenealkylene;
X is a leaving group which can be displaced by nucleo-philes or eliminated in the form of HX by treatment with base, said dye or dye precursor having appended thereto ZNHR
wherein Z is selected from the group consisting of alkylene, arylenealkylene and cycloalkylene, and R is H, alkyl or with Z can be taken together to complete an N containing heterocylic group.