JPS5845696B2 - Photographic film unit for color diffusion transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photographic technology, and specifically to photographic elements, such as color diffusion transfer elements, which employ oxidizing agents.

Color diffusion transfer methods typically involve the use of a photographic element comprising a support, at least one silver halide emulsion layer, and an image dye-forming material contained in or adjacent to said emulsion layer. do.

After exposure, such photographic elements are treated with an alkaline processing solution to produce imagewise distinctions in the element.

As is well known in the art, dye-
The forming material may be initially immobile or initially mobile during processing.

When the immobile dye-forming material is first treated with alkali,
Thereby, a mobile dye or dye precursor can be made imagewise, or the material can be rendered imagewise soluble and thus mobile.

If the material is initially mobile, the processing solution typically renders the material imagewise insolubilizable (and thus immobilized).

Dye-forming materials of this type, whether initially mobile or immobile, are treated with processing solutions and then generally oxidized under alkaline conditions to form image-like distinctions in the element. do.

Such a color diffusion transfer method is described, for example, in US Pat.
98798 and 2559643, the developer is used.

In these US patents, a silver halide latent image is developed with a color developer.

When development occurs, the color developer reduces the exposed silver halide to metallic silver, and the color developer that is oxidized as a result of development forms an immobile part;
On the other hand, unoxidized color developer optionally migrates to the receiving element.

After migration, the color developer contained in the receiver is oxidized.

The oxidized developer is then self-coupled or coupled with a color coupler to form a positive dye image.

A relatively recent photographic process for forming image dyes by oxidation is described, for example, in Belgian Patent No. 792,598.

The oxychromic compounds described in this Belgian patent are chromogenically oxidized to form novel chromophores.

Useful substances belonging to this type have a physical component and an oxychromic component and have the general formula: D-(OC).
(wherein D is a group of a silver halide developer, such as a hydroquinone fraction, and OC is a component that is color-formingly oxidized to form an image dye).

These oxychromic compounds are particularly useful in certain forms of image transfer units in which an initially diffusible oxychromic compound or an initially non-diffusible compound, respectively, is used in combination with a suitable silver halide emulsion.

In order to achieve optimal results when using such oxychromic compounds, they have good stability, can be easily incorporated into photographic elements, and can be incorporated into other components of a given photographic element or film unit. It is desirable to have an oxidant that readily oxidizes the oxychromic component without adverse effects.

Oxidative transformation of oxychromic compounds or other color-forming materials is necessary to achieve the formation of color bodies.

Thus, there is a continuing need in the art for materials that exhibit adequate oxidation capabilities.

For your information, Chang et al., pending U.S. Patent Application No. 367,304, filed June 5, 1973, entitled: PH0TOGRAPHICELEME
NTS C0NTAININGOXIDANTS
I) describes the use of simple nitroxyl free radicals as photographic oxidants.

It would be desirable to provide nitroxy compounds that are even less mobile than most of those described in the Chang et al. application to avoid floating oxidants in the photographic element.

Polymeric nitroxyl group-containing polymers are known in the art.

Those with high nitroxyl content are generally insoluble in water, have low molecular weight, are unstable, or possess a combination of these undesirable properties.

For example, 0, H-Griffith, J, F, W,
Keana, 5-Rottschaefer and T.
, A. Warlick, JAC8, 89, 5072
(1967) described the synthesis and anionic polymerization of monomer (1) and copoly(maleic anhydride-methyl vinyl ether) (molar ratio 1:1) and nitroxyl alcohol (II).
) is described.

has been done.

The N-σ bond of nitroxide possesses an unpaired electron with a characteristic ESR spectrum.

This spectrum is very sensitive to the environment around the N-0 bond, and more information can be obtained about the conformation of the polymer from changes in the ESR spectrum of the nitroxide.

These polymers are engineered to have very low nitroxyl group concentrations, and the methods used to prepare them include, for example, Grignard reagents, nitrosyl chloride, free iodine, lithium metal, etc. Requires handling of hazardous chemicals over extended periods of time.

For example, G, Drefahl, H-H-Horho
ld and -D-Ho f m ann J, Pra
kt-Chem, 37.

137 (1968), mercurylated polystyrene is treated with nitrosyl chloride and the resulting nitroso derivative is converted to hydroxylamine using Grignard reagent and has about 1 nitroxyl group for every 7 styrene repeat units. Oxidation using silver oxide to prepare nitroxyl polymers is described.

Similarly, A, T, Bullock, G-G-C
amerom and P-8mith; Polyme
r and EngineeringScience
e Vol. 12, p. 87 (1972), labeled polystyrene with t-butylnitroxyl groups in 4-6% yield.

Similarly, McConnell U.S. Pat. No. 3453
No. 288 uses the following formula (II
Regarding the use of nitroxyls such as I) and (rV).

All of these known polymers suffer from their instability,
They are not considered suitable for use in the photographic field, either because of their water insolubility or because of the difficulty in preparing their polymers on a commercial scale.

Accordingly, there is a need in the art to provide nitroxyl-containing polymeric compounds for use in photographic elements.

We now provide a set of nitroxyl compounds for use in color diffusion transfer elements and any other photographic element or system in which a stable non-floating oxidant is a necessary or desirable component. We researched and developed the containing polymer compound.

The objects of the present invention are achieved through the use of a set of oxidized nitroxyl-containing polymers in photographic elements, such as color diffusion transfer elements.

Generally, these compounds are used in photographic elements comprising a support having at least one photographic image recording layer and at least one layer having stable free nitroxyl groups of the present invention thereover.

As is well known in the literature, it has one unpaired electron.

A compound containing an N-0 group is a nitroxyl group.

The structure of this part can be considered by juxtaposing the following two resonance structures.

\・■・・e /N −0−\”i −6 / (1) (2) Even though the contribution of structure (1) or (2) to the ground state differs depending on the conjugate effect and the polarity of the medium. good.

Hereinafter, the nitroxyl group will be simply represented by the resonance structure (2) in accordance with generally accepted practice.

Note that electron pairs combined with nitrogen atoms are not specified.

The oxidant of the present invention is a water-soluble polymer containing at least 40 mol% of repeating units represented by the following general formula (3).

In the above formula, n is an integer of 0 or 1, and Q is Represents a divalent bonding group having the following formula (4).

-R3-(L)m -(R')p (4)
In the above formula (4), R3 and R4 are each an alkylene group having about 1 to 6 carbon atoms, and about 6 to 1 carbon atoms.
an arylene group having 2 carbon atoms, an al-zine group having about 7 to 12 carbon atoms (with the structural formula Alk-Ar- or -
Ar-Alk-, in which Alk is the same as the above-mentioned alkylene group and Ar is the same as the above-mentioned arylene group), and R3 can be represented by the following formula (
5) can also be a group represented by: (wherein R5 is the same as defined for R4 above and the carbonyl moiety is directly bonded to the polymer main chain in the formula), m and p are each O or an integer of 1, and L represents an onium salt group, such as a phosphonium group 1
e (R'-P-R' -N -R' X , where R' and X
is the same as the above definition of phosphonium;
(In the formula, R' is the same as defined above, and J is 5 or 6.
or a sulfonium salt group (R'-8-X, where R' and (same as the definition of honium).

Furthermore, in the above formula (3), R represents a hydrogen atom or an alkyl group having about 1 to 6 carbon atoms, R1 represents a hydrogen atom, a carboxy group, or R2
R2 represents a hydrogen atom, an alkyl group having about 1 to 6 carbon atoms, or a carbonyl group when considered as one unit with 1, and (NIOX ) represents a stable free nitroxyl group.

The polymer of the present invention must additionally contain at least 5 mol % of repeating units from which water-solubilizing groups are derived.

Note that the water-solubilizing group referred to here is, for example, an onium salt group (for example, an ammonium salt as described above for L,
sulfonium salts and phosphonium salts), acid groups including acid salt groups (e.g. -C0OH=C00N a ,
COONH4-8OH, SOsNa), etc.

Suitable nitroxyl groups useful in the present invention include the following formula (
6) is included.

-R,''-N-R7(6) In the above formula, R6 has (1) about 1 to 12 carbon atoms, preferably about 3 to 8 carbon atoms, and is in the α-1 position with respect to the nitrogen atom in the formula. represents an alkylene group (including substituted alkylene groups) that has no hydrogen on a carbon atom (i.e., directly adjacent to its nitrogen atom);
or (2) about 6 to 20 carbon atoms, including substituted arylene groups having substituents such as, for example, alkyl groups having up to about 10 carbon atoms, alkoxy groups having up to about 10 carbon atoms, etc. and R7 represents an arylene group having (1) about 1 to 5 carbon atoms, preferably about 3 to 5 carbon atoms, and which is in the α-1 position with respect to the nitrogen atom in the formula; represents an alkyl group, including substituted alkyl groups having no hydrogen, or for example about 10
represents a substituted aryl group having about 6 to 20 carbon atoms with substituents such as an alkyl group having up to 10 carbon atoms, an alkoxy group having up to 10 carbon atoms, a nitro group, etc.

Preferred nitroxyl is a heterocyclic group represented by the following formula (7).

In the above formula, R8, R9, RIO and R11 each contain about 1 carbon atom when considered independent of each other.
R8 and R11 or R9 and RIO can represent a lower alkyl group having 1 to 5 carbon atoms, and R8 and R11 or R9 and RIO can represent a substituted imino group (e.g. -NR', where R' is 1 to about 2 carbon atoms
Imino groups (=
NH) or, if these groups are attached to a carbon atom and are considered integral with that carbon atom, a 5- or 6-membered cycloalkyl or cycloalkenyl nucleus (correspondingly (also includes substituted 5- or 6-membered cyclic rings having about 5 to 25 carbon atoms)
can represent the carbon atoms necessary to form .

When one of Rlo and R11 is considered to be integral with Z,
can represent a cyclic-like double bond formed by Z, in which case R8 or R9 respectively represent (1) a substituted aryl group (e.g. tolyl, aminophenyl, diethylaminophenyl, chlorophenyl) (2) represents an aryl group having about 6 to 25 carbon atoms, including diphenylaminophenyl, or (2) including a substituted amine group (e.g. dimethylamino, methylethylamino, methylphenylamino). In addition, Z represents a nonmetallic atom necessary to complete a 5-, 6-, or 7-membered heterocyclic nucleus with up to two nitrogen atoms.

The above heterocyclic nucleus includes, for example, an alkyl group having 1 to about 25 carbon atoms, an aryl group having 1 to about 25 carbon atoms including substituted aryl groups, an alkyl group, and an amino substituted with an aryl group. amine groups, substituted carbonamide groups, substituted sulfonamide groups,
Imino groups (-N
H)-5 having a substituent such as a hydroxyl group, an oxygen atom, etc.
, 6- or 7-membered substituted heterocyclic nuclei are also included.

Various synthetic methods for preparing nitroxyl groups useful in forming nitroxyl substituents on the polymers of the present invention are described under the heading "Nitroxyl Free Radical (Free N
1troxyl Radicals)”, E, G, Ro
zan-tsev Plenum Press N
ew York 1970.

A large number of stable groups can be prepared from heterocyclic amines that do not have a hydrogen atom on the carbon atom in the alpha position with respect to the nitrogen atom, such as di-t-alkylamines, t-alkylarylamines, etc.

The above-mentioned amines are (1) phosphotungstic acid or (
2) Oxidation with hydrogen peroxide in the presence of vanadium, molybdenum or tungsten salts.

Diarylamines are converted to the corresponding diarylnitroxyls upon oxidation with perbenzoic acid at a temperature of 0°C.

Heterocyclic nitroxyls having one or more heteroatoms (eg porphyrexides) are also known in the art, as are methods for their preparation.

Vinitroxyl and conjugated biradicals are likewise known.

For example, ``Stable free radical organic chemistry (Organic C
Hemistry of Sta-ble Fre
e Radicals)” Forrester et al.
Acad-emic Press, London and New York, 1968, 1st edition, 233, 234,
See also pages 236, 237 and 238.

The term "stable" as used with respect to nitroxyl groups derived from the oxidized polymers of this invention means that these compounds are present as free radicals, at least until the imaging process is substantially completed. This is related to the fact that self-decomposition does not occur for a certain period of time.

Polymers of the invention having nitroxyl groups can be colored, provided that the coloration of the oxidant does not adversely affect the quality of the image.

If the oxidant remains behind the opaque layer and cannot be observed, the coloration of the oxidant will not affect image quality.

Of course, colorless or pale nitroxyl group-containing polymers, which in most cases give rise to only very low Dmin values, are particularly preferred in view of the versatility of such materials.

The colorless or light colored oxidant can be placed anywhere within the film unit that a colored oxidant could be placed.

Furthermore, the light-colored oxidant can be located in a location hidden from view during observation, for example in the receiver element.

Nitroxyl group-containing polymers represented by both formulas (7) and in which the symbols in the formulas have the following meanings are particularly preferred, because these polymers have greater versatility. be.

Preferred explanation of formula (7): R8, R9, R1o and R11 each represent a lower alkyl group having 1 to about 5 carbon atoms when considered independently of each other, and R8 and R11 or R9 and RIO are represents the carbon atoms necessary to form a 5- or 6-membered cycloalkyl nucleus or cycloalkenyl nucleus when considered as one with the carbon atoms in
an alkyl group having ~25 carbon atoms, an acyl group having 1 to about 25 carbon atoms, an amino group, a substituted carbonamide group,
5 having substituents such as substituted sulfonamide group, substituted carbonyloxy group, oxo group (-〇), hydroxyl group, etc.
Represents the carbon atoms necessary to complete a 5- or 6-membered heterocyclic nucleus, including a substituted 5- or 6-membered heterocyclic nucleus.

Generally, when the heterocyclic nucleus formed by Z is a substituted 6-membered ring, the covalent bond (bonding between the troxyl group and the residue of the polymer) is at the 4-position or at the lower position with respect to the nitrogen atom in formula (7). Located in

Polymers of the invention having nitroxyl groups can be prepared according to several methods.

According to one embodiment, as described here for reference,
゛'Research Disclosure (Re5earch D
1 sclosure)” Section 2578, 1973.1
A method similar to that described in February is used.

The method includes alkylating the tertiary amine with an alkylating agent.

According to this method, a tertiary amine or a polymer having repeating alkylating functional groups is reacted with a monofunctional alkylating agent or tertiary amine, respectively, to form an ammonium salt.

The method of the present invention differs from the method of Cohen et al. described in the aforementioned Research Disclosure in that the monofunctional reactive group has a nitroxyl group as a substituent.

This method can be explained as follows. A. When the starting polymer is a tertiary amine B. When the starting polymer is an alkylating agent In the above sections A and B, R in the formula is, for example, an alkyl group having about 1 to 10 carbon atoms. be.

Another method suitable for preparing the polymers of the invention includes copolymerizing a primary amine having a nitroxyl group with a copolymer of maleic anhydride to prepare an N-substituted polyimide in which the substituent is a nitroxyl group. This includes reacting as follows.

In this latter reaction, sufficient carboxyl groups remain unreacted to impart water solubility to the polymer.

Repeating unit of both formulas (3) (n in the formula is 1 and Q
is a simple alkylene or arylene group) can be prepared from the corresponding polymeric acid chloride or its ester with a nitroxyl group-containing amine according to the following formula.

Similarly, oxidized polymers in which Q is a simple carbonyloxyalkyl group, carbonyloxyaryl group, etc. can be prepared from the corresponding polymeric acid chlorides or halide esters and nitroxyl group-containing amines. .

The polymer of the present invention may be a homopolymer or a copolymer.

Suitable copolymers may consist of repeating units as described above and repeating units derived from other addition-polymerizable monomers.

Typical comonomers include ethylene, styrene, acrylic derivatives including acrylic and methacrylic esters (as well as acrylic acids and amides), maleic acid, maleimide, methyl vinyl ether, acrylonitrile, phenyl acrylate, isopropyl acrylate, N- Vinyl-2-pyrrolidone, 2-acetoacetoxyethyl methacrylate, an active methylene-containing monomer curable with conventional photographic hardeners (listed here for reference, e.g., as described in U.S. Pat. Nos. 3,459,290 and 3,488,708). ), sulfonated monomers (e.g., sodium salt of 3-acryloyloxypropane-1-sulfonic acid or sodium salt of 3-methacryloyloxypropane-1-sulfonic acid), and the like.

Whether homopolymers or copolymers are used, the nitroxyl group-containing polymers of the present invention should have relatively high molecular weights, preferably greater than about 5,000.

Additionally, as mentioned above, the nitroxyl group-containing repeat units of the polymer should represent at least 40 mole percent of the total polymer to provide good oxidation properties.

Preferred embodiments of the invention are of the type described herein.
A polymer having 0 mol % or more of repeating units containing nitroxyl groups is used.

Furthermore, as mentioned above, the polymer of the present invention has at least 5 repeating units from which the water-solubilizing group is derived.
It should have mol%.

This water-solubilizing repeating unit may be the same as or different from the nitroxyl group-containing repeating unit.

Polymers containing a water-solubilizing group in the same repeating unit as the nitroxyl group are particularly advantageous from a preparative point of view.

The nitroxyl group-containing polymers described herein can be used in a wide variety of photographic elements or film units.

In certain embodiments, these polymers can be used in photographic elements or film units to provide oxidants for synthesizing image dyes.

The nitroxyl groups of these polymers can be used to form oxidized color developers which, when subsequently reacted with color couplers, form image dyes.

Furthermore, these groups can include, for example, leucoindoaniline,
It can be used to directly oxidize compounds to image dyes as in the case of leucoindophenols, leucotriarylmethanes and other dye precursors.

In one embodiment, the nitroxyl group-containing polymers of the invention are used in a color diffusion transfer process, e.g., when an unreacted color former in an undeveloped or partially developed portion of a photographic element develops color in an exposed layer. After development, it is useful in color diffusion transfer methods in which the color former is imagewise diffused into an image-receiving layer where the color former and oxidized color developer react to form an imagewise distribution of dye.

When the polymeric oxidant of the present invention is included in or combined with an image-receiving layer, the oxidant, the color developer, and the diffused color former are thereby reacted within the element. The dye is formed into an image.

Processes of this kind are further described in British Patent No. 9 of 15 May 1963, of which reference is only made here.
No. 26462.

A specific example of a method for oxidizing a transferred color developer and color coupler to thereby form an image is described in U.S. Pat. No. 25592, which is only cited here.
No. 93 and No. 2,698,798.

Similarly, the oxidants of the present invention can be used in imagining processes based on leucoanthraquinones and other dye precursors which form dyes upon oxidation, or which self-couple upon oxidation and which can be used in developer-based processes such as those that form dyes.

These latter types of processes are further described in U.S. Pat.
No. 892,710 and No. 2,698,798.

Similarly, the oxidants mentioned above have utility in diffusion transfer processes using leuco developers, as discussed in U.S. Pat. Nos. 2,992,105 and 2,909,430, which are only cited here. play.

In another embodiment, the polymer containing nitroxyl groups is used as a developer in a dye developer (i.e., a compound containing a silver halide developing component and a separate portion containing a chromophore of an image dye). Can be used to oxidize parts.

The nitroxyl group selected here must have sufficient oxidation potential to oxidize the developer portion of the molecule, such as the hydroquinone portion.

In this embodiment, the nitroxyl groups attached to the polymeric oxidant form developer components such as quinones, quinoneimides, etc. that are generally completely insoluble in alkaline processing solutions, such as when the dye developer diffuses into the image-receiving layer. It can function to immobilize the dye developer.

In another embodiment, nitroxyl groups can be used to stabilize preformed image dyes.

According to certain embodiments, nitroxyl provides an advantageous increase in the stability of the azo dye transferred to the image-receiving layer.

In yet another embodiment, a photographic element containing an oxidant of the invention can be processed to form an imagewise distribution of the oxidant.

The photographic element can then be contacted with a material that undergoes oxidation to form an image record in the photographic element.

According to one embodiment of this embodiment, a photographic element carrying a silver halide emulsion and an adjacent layer containing a non-diffusible nitroxyl oxidant of the present invention can be developed with a silver halide developer.

Where the silver halide is not developed, the oxidant will be reduced.

The element can then be contacted with a solution of color coupler and color developer to react with the residual imagewise distribution of nitroxyl compounds, thereby forming an image dye.

The nitroxyl group-containing polymer of the present invention is described in the above-mentioned Belky Patent No. 792, which is only cited here.
It is particularly suitable for use as an oxidant in photographic elements or film units containing oxychromic compounds of the type described in No. 598.

Preferred oxychromic compounds are those that undergo chromogenic oxidation to form photographic image dyes.

In one embodiment, the oxidized nitroxyl of the present invention is incorporated into a photographic element containing an oxychromic compound of the formula:

photographic color couplers, such as phenolic couplers, which are bonded to the nitrogen atom via a carbon atom in
A pyrazolone coupler, a pyrazolotriazole coupler, a coupler having an open-chain ketomethylene group, etc., Ar is an arylene group having 6 to 20 carbon atoms, including substituted and unsubstituted arylene groups, a fused ring arylene group, etc. is an amino group, including a substituted amine, a hydroxyl group, or a group of the following formula: (wherein, Rb is a group having 1 to 12 carbon atoms,
(can be an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, etc.), and Ra is a hydrogen atom or a group of the following formula: (wherein R6 is the same as the above definition, preferably is a polyhalogenated alkyl group), and T is a silver halide developer which is (1) or an aromatic group polysubstituted with a hydroxyl group, an amino group or a substituted amino group, or (2). ) represents a group such as an oxidizable releasing group (ie, a group that can be oxidized to facilitate subsequent group release) or a group that can be oxidized to prevent normal group release under processing conditions.

When T is a silver halide developer, the resulting compound is preferably initially mobile.

When T is an oxidizable releasing group, the resulting compound is preferably initially immobile.

The nitroxyl oxidants of the present invention can be used in processing solutions when it is desired to effect oxidation at this location of the diffusion transfer film unit.

More generally, the oxidants of the present invention are located near or within the image-receiving layer of a diffusion transfer film unit using another image dye-forming material as described above.

Image transfer film units may be selected from among those described in the following patents, all of which are cited here: U.S. Pat.
No. 543181; No. 2983606, No. 3227
No. 550, No. 3227552, No. 3415644
Canadian Patent No. 674082 and Belky Patent No. 757 issued April 23, 1971.
No. 959 and No. 757960.

The nitroxyl oxidant is generally about 0.0
It is present in a concentration of 1 to about 0.1 molar.

If the oxidant of the present invention is not included in the processing solution, it is generally coated in at least one layer containing a binder, such as gelatin, poly(vinyl alcohol), and the like.

7 Of course, the nitroxyl group-containing polymers described herein can also be one of several components included in a given layer.

For example, if a nitroxyl polymer is used in the color diffusion transfer unit, the polymer can be included in the mordant layer.

Generally, these polymers contain about 4 to 551111 milliequivalents depending on the milliequivalents of nitroxyl groups contained in the chosen polymer.
It is covered with the amount of coverage of the I/D door 2.

However, a sufficient amount of nitroxyl group-containing polymer should be present to effect substantially complete oxidation.

It goes without saying that the amount of polymer required to achieve complete oxidation will depend on the amount and type of oxychromic compound used.

In a preferred embodiment, the nitroxyl polymer is used in an image transfer film unit that is designed to be processed in a single processing solution, whereby the resulting positive-working image is preferably separated by a silver halide recording layer and an image-receiving layer. are viewed through the transparent support using an opaque background, where all of the components remain laminated between two dimensionally stable supports after processing.

Suitable image transfer film units in which the oxidants of this invention find utility generally comprise the following components:

(1) A support and at least one silver halide emulsion-containing layer provided above the support, in which the emulsion is combined with an image dye-forming material, preferably at least three silver halide emulsion-containing layers ( one of these layers contains a blue-sensitive silver halide emulsion, one contains a green-sensitive silver halide emulsion, and one contains a red-sensitive silver halide emulsion). Element; (2) an image-receiving layer that can be positioned on a separate support superimposed or adapted to be superimposed on said photosensitive element; and (3) for containing an alkaline processing composition, the contents of which are located within the film unit. The means by which it is discharged.

When the image-receiving layer is coated on the same support as the photosensitive silver halide layer, the support is preferably a transparent support and the opaque layer is preferably coated on the same support as the image-receiving layer and the photosensitive silver halide layer. and the alkaline processing composition preferably contains an opacifying material, such as carbon or dye, which is then applied to the interior of the film unit to form a dimensionally stable support or cover. It is discharged between the sheet and the photosensitive element.

In certain embodiments, the cover sheet may be superimposed or superimposed over the photosensitive element.

The image receiving layer can be coated onto the cover sheet.

According to certain preferred embodiments in which the image-receiving layer is located within the photosensitive element, a neutralizing layer is located above the cover sheet.

The means for containing the alkaline processing solution can be any means known in the art for this purpose, including placing the contents of the container at the desired discharge point into the film unit. a rupturable container located on or within the photosensitive element and adapted to pass between a pair of juxtaposed rollers to effect evacuation of the contents into the film unit; This includes hypodermic syringes.

Silver halide emulsions useful in the present invention are widely known to those skilled in the art and are described, for example, in the "Product Licensing Index".
Index), Volume 92, December 1971, Publication 92
32. Page 107, Section 1, “Types of Emulsions”
on types)”.

These emulsions are particularly described on page 107, section 6, of the above-mentioned document.
Chemical sensitization
on )” and pages 108-109, Section XV, “Spectral sensitization”
It may be chemically and spectrally sensitized as described in ``.

These emulsions are described in Section V, Antifoggants and Stabilizers, page 107 of the above-mentioned document.
By using the substances described in ``5ta-bilizers'' it is possible to protect against fog formation during storage and to stabilize against loss of sensitivity.

Furthermore, these emulsions are described in pages 107-108 of the above-mentioned document, Section
odi f 1ers)”, Section ■, 1 Hardening agent (Har
deners)” and Section 6, Coating Aid (C
development modifiers, curing agents, and coating aids as described in "Oating Aids".

These emulsions and other layers included in the photographic elements used in this invention are described on page 108, section
6 Plasticizers and lubricants
109, Section XVI, 6 Absorbing and r Photopigments
It may contain plasticizers, vehicles, and gloss dyes as described in "Fi-1terdyes".

These emulsions and other layers included in the photographic elements used in this invention are described in page 109, section
may contain additives that are incorporated using the techniques described in ``Coa n)'', and those additives may also be incorporated using the techniques described in ``Coa
Coating can also be accomplished by using various techniques described in "Ting Procedures".

(All disclosures in the above documents are provided for reference only.

) Any material may be used in the present invention as the image-receiving layer so long as it provides the desired function of mordanting or otherwise fixing the dye image.

Of course, the particular material chosen will depend on the dye used for mordant.

If acidic dyes are to be mordanted, the image-receiving layer may be a basic polymeric mordant, such as vinyl methyl as described in Minsk U.S. Pat. No. 2,882,156 (issued April 14, 1959). Polymers of aminoguanidine derivatives of ketones, and e.g.
Basic polymeric mordants such as those described in U.S. Pat.

Additional mordants include cationic mordants, such as quaternary nitrogen atoms and at least two aromatic nuclei for each quaternary nitrogen in the polymeric cation (i.e., for each positively charged nitrogen atom). at least 2
includes a polymer compound consisting of a polymer (having 1 aromatic nucleus) and substantially free of carboxy groups.

Useful mordants belonging to this type are derived from units represented by the general formula below and units of at least one ethylenically unsaturated monomer in copolymerizing relationship with the units.

In the above formula, R and R each represent a hydrogen atom or an alkyl group having 1 to about 6 carbon atoms, and R is a group having at least one aromatic nucleus, such as a phenyl group or a tolyl group. Q/ is 1 carbon atom
A divalent alkylene group having ~6 atoms, a divalent arylene group, a divalent aralkylene group, a divalent arylene group O
O 111 can be an alkylene group, -C-OR17--QC-R17 or 1 -C-NH-R17- (in which R17 is an alkylene group).

Alternatively, R13 can be Q', R, R and R can be lower alkyl or aryl groups, or R1
4 and R and the nitrogen atoms to which these groups are attached represent the atoms and bonds necessary to combine with Q' to form a heterocycle containing a quaternized nitrogen, and Xe represents the positive salt formation. A monovalent negative salt-forming group or atom that is in an ionic bond with a group.

In this case, said polymer is substantially free of carboxy groups and the positive salt-forming groups of said polymer comprise at least two aryl groups for each fourth nitrogen atom in said polymer. .

These preferred polymeric cationic mordants are further described in the aforementioned U.S. Pat. No. 3,709,690, which is only incorporated herein by reference.

Other mordants useful in the present invention include S pra
U.S. Patent No. 2,484,430 to Gue et al.
These include poly-4-vinylpyridine, a 2-vinylpyridine polymer of metho-p-)luenesulfonic acid and similar compounds, and cetyltrimethylammonium bromide, as described in the US Pat.

Effective mordants are further described in Whitmore, U.S. Pat. No. 3,271,148 and Bush, U.S. Pat. No. 327.
1147 (both published September 6, 1966).

In addition, the nitroxyl group-containing polymers of the present invention containing quaternary amine nuclei can be used as mordants for acidic dyes without the need for any other mordants.

Accordingly, many of the polymeric compounds of the present invention, as oxidants,
And it can play both roles as a mordant for image dyes.

Next, in order to further facilitate understanding of the present invention, the present invention will be explained according to the following Preparation Examples and Examples.

Preparation Example 1 Poly(N,N-dimethyl-N-(2-ethylmethacrylic)-N-(1-(N-(2,2,6.

6-tetramethyl-4-piperidine-1-oxyl)acetamide)) Ammonium chloride] Intrinsic viscosity [η] Benzene - 0.40 (Note: All intrinsic viscosities listed here are 0.25 g for the specified solvent bath 11d1. 3,18. ! 9(0,0
202 mol) of poly(2-dimethylamine ethyl methacrylate) and 5,O,! i+ (0,0202 mol) of 4-(α-chloroacetamido)-2,2,6,6-tetramethylbiperidin-1-oxyl in 3.0 rIll
A solution of N,N-dimethylformamide was heated on a steam bath under nitrogen for 3 hours.

The polymer was separated by precipitation in ether, collected by filtration, and dissolved in 30 rrLl of methanol.

The polymer was again precipitated in ether (re-precipitated), collected by filtration, and dissolved in 30-mL water while still wet.

The solution obtained above was then briefly placed on a rotary evaporator to remove traces of ether.

An aqueous solution (solid content: 18%) of oxidized polymer 1 was obtained.

The theoretical values and actual values calculated for C1, H35N304C1 are as follows.

Calculated value C56,4; H8,7; N10.4; C18
,8 actual measurement value C56.4; H8.6; N 10.4
C18,2 Preparation Example 2 3.7:l (0,0202 mol) of poly(N
-(3-dimethylamino-1,1-dimethylpropyl)
Preparation 1 was repeated using 5.0 g (0.0202 mol) of 4-(α-chloroacetamide)-2,2,6,6-tetramethylpiperidine-1-oxyl.

The polymer was dissolved in 70% water to yield a clear solution containing 9.9% solids.

The theoretical values and actual values calculated for C2□H4oCIN403 are as follows.

Calculated value C58,4; H9,3; Nl 3.0; C1
8,2 actual value C54,9; H9,O; N 1 a2
; C16,9 Preparation Example 3 Poly(N-[3-propylacrylamide]-N,N-
Dimethyl-N-[1-(N-(2,2°6.6-tetramethyl-4-piperidine-1-oxyl)acetamide)]ammonium chloride) [ηIDMF -0, 3,15.9 (0,0
202 mol) of poly[N*20-(3-dimethylaminopropyl)acrylamide] and 5. i (0,02
02 mol) of 4-(α-chloroacetamide)-2,2
, 6,6-tetramethylbiperidin-1-oxyl.

However, in this case the product was isolated by first precipitation in acetone, subsequent dissolution in 30-methanol, and reprecipitation in ether.

Then, when the polymer was dissolved in 35rrIl of water, 1
A clear solution containing 9.9% solids resulted.

C1, H3, C1N40. The calculated theoretical values and actual measured values are as follows.

Calculated value C56,4; H8,9; N13.9; C18
,8 actual measurement value C56.5; H9.6; N 13.8
; C18,2 Preparation Example 4 2.62.9 (0,0101 mol) of poly[styrene-
3-N-(3-dimethylaminopropyl)acrylamide) (1:1) and 5.1 (0,0202 mol) of 4-
A reaction was carried out in the same manner as in Preparation Example 1 using (α-chloroacetamide)-2°2.6,6-tetramethylbiperidine-1-oxyl.

However, in this case the solution was heated on a steam bath for 5 hours.

The final product was dissolved in 30 rnl of water and found to be 9.9
A clear solution containing % solids was obtained.

The theoretical values and actual values calculated for C, 7H4, and CI N403 are as follows.

Calculated value C63,8; H8,7; C17,0; N 1
1.0 Actual value C66,8; H8,2; C15,3; N
10.0 Preparation Example 5 Poly(vinylbenzyl chloride-3-N-vinylbenzyl-N,N-dimethyl-N-[2-ethyl-4-(2,
2,6,6-tetramethylbiperidin-1-oxyl)
urea] ammonium chloride) (1:1) m copolymer [η] benzene = 3, 10.9 (0,
0203 mol) of poly(vinylbenzyl chloride) and 3.0 g (0.0102 mol) of N-(2-dimethylamineethyl)-N'-(2,2,6°6-tetramethyl-4-piperidine- 1-oxyl) urea 30r11
A solution of 1 dissolved in methoxyethanol was heated at a temperature of 100° C. for 3 hours.

The polymer was precipitated in acetone, collected by filtration, and dissolved in 30-methanol.

reisolating the polymer by precipitation in ether;
Collected by filtration and while still damp 50m/
dissolved in water.

The aqueous solution obtained above was briefly placed on a rotary evaporator to remove traces of ether, resulting in an aqueous solution containing 10.8% solids.

The theoretical values and actual values calculated for C3□H47C12N402 are as follows.

Calculated value C65,1; H8,0; H9,5; C112,
0 actual measurement value C62,4; H8,2; H8,O; C111
, 6 Preparation Example 6 PolJ[N-vinylbenzyl-N,N-')methyl-N
-(4-acetamido-2,2,6,6tetramethylbiperidine-1-oxyl)ammonium chloride] [η] 3,82.9(0,
025 mol) of poly(vinylbenzyl chloride) and 7
．． The reaction was carried out in the same manner as in Preparation Example 5 using 1 (0,0273 mol) of 4-(α-dimethylaminoacetamide)-2,2,6,6tetramethylpiperidine-1-oxyl.

The final product was dissolved in 60rnl of water and 11.
C22H3 resulting in a clear solution containing 3% solids
, N302CI, the calculated theoretical values and actual measured values are as follows.

Calculated value C64,6; H8,6; N 10.3;
C18,7 actual value C64,3; H8,9; N10.1
;C17,9 Preparation Example 7 Copoly [Styrene; N-vinylbenzyl-N.

N-dimethyl-N-(4-acetamido-2°2.6,
6-tetramethylpiperidine-1-oxyl) ammonium chloride] [η] 6,4.9(0,02 with DMF=0.75
5 mol) copoly(styrene vinylbenzyl chloride)
(1:1) and 7. O,! i+ (0,0273 mol)
4-(α-dimethylaminoacetamide)-2゜2.
6.6-tetramethylbiperidin-1-oxyl to 75
A solution dissolved in 1nl of benzyl alcohol was heated to 100°C.
The mixture was heated under nitrogen for 3 hours at a temperature of .

Separate the polymer by precipitation in acetone and r
It was collected by filtration and dissolved in 501 ml of methanol.

The product was reprecipitated in ether, collected by filtration, and dissolved in 90 yards of water while still wet.

The solution obtained above was briefly placed on a rotary evaporator to remove traces of ether, resulting in a concentration of 9.4%.
An aqueous solution was obtained containing a solid content of .

The theoretical values and actual values calculated for C3oH43N302C1 are as follows.

Calculated value C70,2; H8,5; H8,2; C17,0
Actual value C69,8; H8,2; H7,9; C15
, 1 Preparation Example 8 Poly [ethylene-3-N-(2,2,5,5-tetramethyl-3-pyrrolidine-1-oxyl)maleimide] 3°55.9 (0,029 mol) copoly [ethylene / maleic anhydride] (1:1) and 5.0 g (0,
A solution of 3-amino-2,2,5,5-tetramethylpyrrolidine-1-oxyl (029 mol) dissolved in 30-N,N-dimethylformamide was dissolved at a temperature of 100°C for 30
Heated for minutes.

The polymer was precipitated in ether, collected by filtration, and dissolved in 50°C of water while still wet.

The solution obtained above was briefly placed on a rotary evaporator to remove traces of ether, resulting in an aqueous solution containing 10% solids.

The theoretical values and actual values calculated for C14H23N204 are as follows.

Calculated value C59,3; H8,2; H9,9 Actual value C56,9; H8,8; N10.4 Preparation example 9 Copoly[ethylene; N-(2,2,6,6-tetramethyl-4-piperidine) -1-oxyl) 3.55 g (0,
029 mol) copoly [ethylene/maleic anhydride'
J (1:1) and 7.0.9 (0,041 mol) of 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl dissolved in 35-N,N-dimethylformamide. The solution was heated at a temperature of 130° C. for 30 minutes.

The polymer was precipitated in ether and 50772/! of methanol and reprecipitated in ether.

The polymer was collected by filtration and dissolved in 80% water while still wet.

The solution obtained above was briefly placed on a rotary evaporator to remove traces of ether, resulting in an aqueous solution containing 8.6% solids.

The theoretical values and practical values calculated for C15H25N204 are as follows.

Calculated value C60,7; H8,4; H9,8 actual value C58,7; H9,2; H9,3 Example
1 The oxidants listed in Table 1 below were tested as follows.

7577Z? 1 25111Ii/ft of Seratin dissolved in diethyl lauramide and 50
A matrix element consisting of a transparent film substrate support having a layer of oxychromic compound of "P/ft. brought into existence.

The receptor element comprises a first oxidizer (prepared according to the preparation examples numbered in Table 1 below) in 100/729/ft of gelatin.
layer and 200” in a ceftin of 9/ft.
a second layer comprising mf/ft titanium dioxide (
(above the first layer) on top of a transparent film substrate support.

The treatment set was a 7.5% potassium hydroxide solution containing 2.5% oxyethylcellulose thickener.

After contacting the two elements, the oxychromic compound migrates from the IJ flux through the processing composition and the titanium dioxide layer to the oxidant layer (which was also the mordant layer) of the receiver. It was great.

This oxychromic compound was then oxidized by an oxidized nitroxyl group-containing polymer and converted into the corresponding dye.

The dye thus formed could be seen through the transparent support against the background of a white titanium dioxide layer.

For reference, the types of oxychromic compounds and oxidants as well as the color and density of the dyes contained in the image receptor are listed in Table 1 below.

Incidentally, the structural formula of the oxychromic compound is described next to the examples.

Example 2 The procedure of Example 1 was repeated using the oxidant described in Preparation Example 8.

Since this oxidant does not contain a quaternary amine nucleus, 10
07II9/ft2 of gelatin with 200 μ/ft of copoly[styrene: N,N-dimethyl-N-benzyl-
A mordant layer comprising N(3-maleimidopropyl) ammonium chloride was inserted between the oxidant layer and the support.

matrix and image receptor in the presence of a developer composition.
After 0 seconds of contact, oxychromic compound A has a temperature of 0.
Oxychromic Compound B produced a yellow dye with a density of 7, while Oxychromic Compound B produced a magenta dye with a density of 2.4.

Example 3 A laminated monolithic color transfer photographic element was prepared as follows.

(Detailed explanations of specific components are given after the examples.

) ■) Transparent polyethylene terephthalate support; 2)
3) Dye mordant/oxidant layer containing 100 µ/ft2 of gelatin and 200 µ/ft2 of the nitroxyl group-containing oxidant described in Preparation Example 4; 3) 2000 µ/ft2;
t2(7) Titanium dioxide and 200772? 4) a layer containing 20 mg/ft of Seratin; 4) a layer containing 20 mg/ft of carbon opacifying agent and 156 mg/ft of Seratin; 5) a layer containing 75 mg/ft of Gelatin;
mq/ft2 of 2°5-G sec, -dodecylhydroquinone and 237'! P/ft layer containing tricresyl phosphate; 6) 70 m97 ft2 of red-sensitive silver bromoiodide emulsion, 230 m'il/ft Nocera-f-7,73 based on silver;
42 m dispersed in 97 ft2 of diethyl lauramide
/729/ftno compound E, 15772? /ft
(7) 5m' dispersed in tricresyl phosphate!
/ft of 5(2-cyanoethylthio)-1-phenyltetrazole and '0;10m'i/ft2no5,6
, 7,8-tetrahydro-58-methano-14-naphthalene diol; 7) 300"i!/ft20) Serafone, 70"9
/ft" (D2.5-sec, -layer containing 30 m/ft of magenta gloss dye dissolved in dodecylhydroquinone and 50 m/ft of diethyl lauramide; 8) 70 m?/ft based on silver. /ft2 of green-sensitive silver bromoiodide emulsion, 230 ■/ft2 of gelatin, 64 m'i/ft
54 μ/ft2 dispersed in diethyl lauramide
of oxychromic compound B, 5T119/ft" of 5-(2-cyanoethylthio)-1-phenyltetrazole dispersed in 15/ft2 of tricresyl phosphate and 5.6,7.8 of 10TrI9/ft". -tetrahydro-5,8-methano-1,4-naphthalene diol; 9) 300 µ/ft of seratin, 70 µ/ft of 2.5-sec, -dodecylhydroquinone, and 28
10 dispersed in diethylrauramide with η/ft,
10) Blue-sensitive silver bromoiodide emulsion of 70 wj/ft2 based on silver, ceratin of 210 m9/ft, 106"//f
64■/ft dispersed in diethyl lauramide of t2
Oxychromic Compound A of 2, 5-1/ft2 5-
(2-Cyanethylthio)-1-phenyltetrazole and 10772! //ft2 of a layer containing 5.6,7.8-tetrahydro-5,8-methano-1,4-naphthalene diol; and 11) a layer containing 5 o1119/ft2 of gelatin.

A transparent cover sheet for the above element was prepared as follows.

1) Transparent polyethylene terephthalate support; 2)
900”if/ft (D cellar f-7,900m
a layer containing 'i/ft of polyacrylic acid and 760 η/ft of imidazole; and 3) 1140 η/ft of cellulose acetate and 60 η/ft.
ft of copoly(styrene/maleic anhydride).

Exposure is applied to the photographic element through a stepped density multicolor test object, the transparent cover sheet described above is superimposed over the photographic element, and the photographic element is exposed between a pair of juxtaposed rollers having a gap of approximately 8 mils. The bod containing the opaque processing composition was ruptured by passing it through the film unit, releasing its contents between the cover sheet and the photosensitive element.

The treatment composition used here was as follows.

Potassium hydroxide 5111/11 oxyethyl cellulose 30 g/l Potassium bromide
4011/1 α-Benzylpicolinium bromide 15g/15678-tetrahydro5.8-methano-1,4-naphthalenediol 15g/II carbon
409/1 Add water
After approximately 1-2 minutes, a well-resolved color image with good color reproduction was observed through the transparent support of the laminated monolithic element.

Oxychromic compounds A-E cited in the previous examples
The structural formula is shown in Table 2 below.

Although the invention has been described in detail with particular reference to preferred embodiments thereof, it will be understood that various changes and modifications may be made within the spirit and scope of the invention.

Claims (1)

Claims: 1. A photographic film unit for use in a color diffusion transfer process, comprising: (a) a support having above a light-sensitive silver halide emulsion in which an image dye-forming material is combined; (b) an image dye-receiving layer containing an oxidant; and (b) an image dye-receiving layer containing an oxidant.
C) means for releasing an alkaline treatment composition into the interior of the film unit, wherein the oxidant has any one of the following general formulas:
A photographic film unit for color diffusion transfer, which is a water-soluble polymer comprising at least 40 mole percent of repeating units represented by: