JPS6023854A - Photographic element - Google Patents

Abstract

PURPOSE:To obtain a photographic element for a color diffusion transfer process having superior image retentivity and mordanting power by incorporating a polymer having specified imidazole groups as a mordant. CONSTITUTION:A water-dispersible polymer consisting of units represented by formula I (where A is a unit of a copolymerizable monomer having two or more ethylenic unsatd. groups; B is a unit of a copolymerizable alpha,beta-ethylenic unsatd. monomer; R1 is H or CH3; each of R2 and R3 is H, alkyl or aryl; L is a bivalent combining group; x is 0.5-6.0mol%; y is 0-79.5mol%; and z is 20- 99.5mol%), e.g., a polymer having units represented by formula II is incorporated into an image receiving layer as a mordant to obtain a photographic element having high image retentivity and superior mordanting power. When a color image substance is diffused in the image receiving layer during development, a fine dye image of high density is formed in a short time.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to photographic elements containing layers containing novel polymers, and more particularly to photographic elements for color diffusion transfer using the polymers as good mordants in dye pools. It is about elements.

(Prior art) The color diffusion transfer method includes a photosensitive element having a photosensitive layer containing a silver halide photographic emulsion, and an image receiving element that transfers substances diffused from the photosensitive element during development processing to form a color image. There are those in which the photographic elements of Fl et al. are integrated, and those in which these photographic elements can be separated separately. In either case, in a light-sensitive element, a light-sensitive layer containing a silver halide photographic emulsion is imagewise exposed to form a latent image, which is developed by a processing solution, and at the same time a color image-forming material forms an image-wise color image material. do. At least a portion of this color image material diffuses and is transferred to an image receiving layer in an image receiving element provided superimposed on the emulsion layer to form a dye image. It is known to use various monomers as mordants to prevent the dye image formed in the image-receiving layer from migrating to other locations. Some of these polymer materials include polymers with quaternary nitrogen atoms, as described in, for example, U.S. Pat. No. 3,709,690, U.S. Pat. Although known, these polymers cannot be said to have sufficient performance. That is, the image-receiving layer using this type of polymer as a mordant has poor image storage stability, and the color images tend to fade over time.

For example, US Patent 4. '273,853, 4,282.
,.

No. 305 and British Patent No. 2,011,912 describe polymers containing imidazole groups, but these polymers cannot be said to have sufficient feminine abilities either.

That is, the feed polymer used as a mordant in the image-receiving layer may itself migrate to other hydrophilic colloid layers. This transferred mordant stains the diffused acidic dye and inhibits the formation of a color image in the image-receiving layer. Further, the dye attached to the transferred mordant may be later desorbed and cause color staining.

On the other hand, even if the compound satisfies these conditions, the film-forming ability is poor and the viscosity of the coating composition is extremely high, making uniform and uniform coating difficult. However, there were problems in that the stability of the resulting color image was insufficient.

In order to overcome the above-mentioned drawbacks, extensive searches have been made for new mordant polymers for use in image-receiving layers.

(Objects of the Invention) The present invention relates, in part, to a photographic element in a color diffusion transfer process containing this polymer as a mordant; It is to provide. A second object of the invention is to provide a photographic element having an image-receiving layer with excellent mordanting ability.

A third object of the present invention is to provide a photographic element in which a color image material diffused into an image-receiving layer during development can be mordanted to obtain a good dye image with high density in a short period of time.

A fourth object of the present invention is to provide photographic elements containing polymers that have excellent mordanting ability without adversely affecting photographic performance.

A fifth object of the present invention is to provide a photographic element containing a mordant and the polymer used in No. 17 which has excellent film-forming properties on its own and also has excellent film-forming properties when used with a bulk binder. .

(Structure of the Invention) The objective of the present invention is achieved by a photographic element containing a unit represented by the following general formula (I) and containing a substantially water-dispersible polymer. Ru.

General formula (error R.

10+9+B-) (-CH,-C' I In the above formula, R1 is a hydrogen atom or a methyl group, and R1
and R3 is a hydrogen atom, an alkyl group or an aryl group.

The alkyl group represented by R2 and R3 has 1 to 4 carbon atoms.
The alkyl group may have a substituent, and the substituent is an alkyl group or an aryl group in which the total number of carbon atoms of each of R2 and R5 is within the range of 6 to 12. It is preferable that.

Furthermore, the aryl group represented by R2 and - has 6 to 6 carbon atoms.
12 is preferable, and the aryl group may also have a substituent, and the substituent is the same as the substituent for the alkyl group.

L is a divalent linking group, preferably a lower divalent linking group, and a complex linking group represented by -L, -, and -. In the composite linking group -L, -L, --, is the imidasol-side linking group of general formula (I).

L1 may be an arylene group, an acid amide group or an ester group, preferably a phenylene group, a carbonylamino group or a carbonyloxy group.

Also, it is an alkylene group. The alkylene group d preferably has 1 to 4 carbon atoms, and the total number of carbon atoms in idL as a substituent for the alkylene group is preferably 7 to 12.

In addition, as an example of the case where the alkylene group has a substituent, i
It contains an arylene alkylene group.

Further, the bonding position of the imidazole side linking group L2 of the composite linking group to the imidazole ring may be any position, but preferably t and < are the 1st positions.

The copolymerizable monomer A having at least two ethylenically unsaturated groups is preferably a monomer represented by the following general formula (11).

General formula (If) 4 (CH,=C+ all where n is an integer larger than 2, preferably 2, R4 is selected from a hydrogen atom and a methyl group, and R, represents n bonding groups. For example, an alkylene group (e.g., ethylene group, trimethylene group, phenylethylene group), alkylidene group (e.g., ethylidene group, ingropylidene group), alkylidine group (e.g., methylidine group, trichloroethylidene group), arylene group. (e.g. phenylene group), -coNn-, -so, NH-1
-coo-1 Furthermore, a linking group combining various groups [e.g. methyleneoxycarbonyl, ethylenebis(oxycarbonyl), phenylenebis(oxycarbonyl),
4.4'-isopropylidene bis(phenyleneoxycarbonyl), 1,2,3-propanetriyltris(oxycarbonyl), cyclohexylene bis(methyleneoxycarbonyl), methyleneoxymethylenecarbonyloxy, methyleneiminocarbonyl, oxymethylene oxy, ethylenebis(oxyethyleneoxycarbonyl), ethylidentris(oxycarbonyl)].

Suitable examples of monomers represented by general formula (■) include divinylbenzene, allyl acrylate, N-allyl methacrylamide, 4,4'-isopropylidene diphenyl diacrylate, 1,3-butylene dimethacrylate, 1 .4-Cyclohexylene dimethylene dimethacrylate, diethylene glycol dimethacrylate, civinyloxymethane, ethylene diacrylate, ethylidene dimethacrylate, 1,6-diacrylamide hexane, N,N'-methylenebisacrylamide neopentyl dimethacrylate, phenylethylene dimethacrylate methacrylate, tetraethylene glycol dimethacrylate,
Tetramethylene diacrylate, 2,2,2-trichloroethylidene dimethacrylate, triethylene glycol dimethacrylate, ethylidene trimethacrylate,
Propyridine triacrylate, vinyl allyloxy acetate, vinyl methacrylate, ″1-vinylogycy 2
- Mention may be made of allyloxyethane. Most preferred is divinylbenzene.

Examples of useful copolymerizable α,β-ethylenically unsaturated monoblocks B include alkenes (e.g. ethylene, globylene, 1-butene, inbutene, 2-methylpentene, alkafolines (e.g. halides).

1.4.4-tetramethylbutadiene, isoprene],
Styrenes (e.g. styrene, α-methylstyrene, p
- monoethylenically unsaturated esters of fatty acids containing chlorstyrene, p-methylstyrene, m-ethylstyrene (e.g. vinyl acetate, allyl acetate), esters of ethylenically unsaturated mono- or dicarboxylic acids (e.g. 90% methacrylic acid of methyl methacrylate) (lower alkyl esters of acrylic acid such as butyl acrylate, diethyl methylene malonate), rhodanized olefins such as vinylidene chloride, dienes such as butadiene, nitrides such as acrylonitrile, acrylamide , acrylamides such as methacrylamide and diacetone acrylamide, vinyl ethers such as vinyl ethyl ether, N-vinylpyrrolidone and the like, fluorinated vinyl compounds such as CF, =CF, and the like. Among these, preferred are styrenes and esters of ethylenically unsaturated monocarboxylic acids.

In the general formula (I), χ, y, and J are copolymerized mol% of each monomer unit, and 0.5≦χ≦6.0 0≦y≦79.5 Add≦J≦99 The value is in the range of .5. Also, regarding J, make sure that 5≦J≦
It is 70.

3 Each monomer unit represented by is 2I.

Within the mole% range defined by y and 7,
Each glaze may contain two or more monomer units.

The polymer according to the invention is a water-dispersible polymer, and is characterized by having a monomer unit having an imidazole group in the portion forming a side chain as shown in the above general formula (I). .

Owing to these characteristics, the above-mentioned object of the present invention has been achieved, and monomers structurally similar to the above-mentioned monomer units according to the present invention described in British Patent No. 2,011.912. It has a better mordanting ability than polymers having units such as -C)T, -CB-, and it is easy to obtain water-dispersible polymers during the manufacturing process. It is advantageous in

The monomer used in emulsion polymerization is generally preferably liquid in the reaction system at the temperature during polymerization. Furthermore, even in liquid form, emulsion polymerization of monomers with different degrees of hydrophilicity requires different emulsifiers, polymerization methods, etc., and different methods must be used.
If the hydrophilicity is too high, polymerization stability during emulsion polymerization will be poor and a water-dispersible polymer will not be produced. Therefore, when selecting a monomer, in addition to the melting point of the monomer, hydrophilicity, copolymerizability,
Factors such as thermal stability, chemical reaction, etc. must be considered.

The above-mentioned monomers used to produce the polymer according to the present invention are also excellent in this respect.

The above emulsion polymerization is generally carried out in the presence of an anionic surfactant and a polymerization initiator. Anionic surfactants such as sodium lauryl sulfate, sodium salts of sulfuric acid condensates of alkylphenols and ethylene oxide, and Rohm & Haas (Rohm & Haas)
Trito by M & Hass Co.
n) 770 etc.

A preferred example of the first initiator is an alkali metal salt of azobiscyanovaleric acid.

In a solid-pore emulsion polymerization system, azobis/anovaleric acid and an alkali (eg, potassium hydroxide or sodium hydroxide) may be added. The amount of alkali may be sufficient to neutralize the acid portion of azobiscyanovaleric acid, but it is also possible to add more than that amount. These neutralize the sulfuric acid derived from the decomposition product of the surfactant and reduce its influence on the tertiary amine moiety. Redox-based free radical initiators described in U.S. Pat. No. 3,958,995, such as potassium persulfate-bisulfite) IJum, ammonium persulfate-bisulfite) IJum, hydrogen peroxide-Fe2+, have polymerization stability;
Unfavorable in terms of coloring, etc. The temperature for emulsion polymerization cannot be uniformly determined due to the relationship with the physical properties of the monomers, but it is preferably a temperature at which the polymerization reaction system is in a liquid state and is easily emulsified and dispersed by stirring, usually 65 to 90°C. ,
Furthermore, 70-85 degreeC is preferable.

Here, "water-dispersible polymer" refers to a polymer that appears transparent or slightly cloudy when viewed with the naked eye, but is dispersed in fine particles when examined under an electron microscope. Say something.

Also, "substantially aqueous" means that the main portion of the dispersion medium in the dispersion composition is usually 90% or more, preferably 95% or more.
It means that t% or more of water is water. The remainder of the dispersion medium may be, for example, methanol, ethanol, methylcellosolve, dioxane, or N.

Hydrophilic organic solvents such as N-dimethylformamide can be used alone or in combination.

The molecular weight of the copolymer according to the present invention is arbitrary, but low molecular weight I is unfavorable from the viewpoint of mordant ability and dye fixing property, and conversely, when the molecular weight is large, it is unfavorable from the viewpoint of film-forming property. It's not good so about 5,000 to about], 00
A value between 0.000 is preferred, and good results are obtained between about 10.000 and about 500.000.

Next, typical examples of the polymer of the present invention will be listed, but the present invention is not limited to these.1. It's not something you can do.

Exemplary polymer χ:y:,+=4:28:68 +I:y:J-4=26:7°CH.

+I: y: IP=4:26:705・(J(
8! l:n,'lt:i≧4:cloth:ka:kaku2:ν
:, 4=4:48:48 CH.

(-CH, -CH, Su2:n:J24:48:4Bz:7: ) =4:48:48z:y:
z-4:48:48 1:y: )=4:48:48jl:y:
)=4:48:48χ:y:)=4:4
8:48z:y:J=4:48:48z:y:J=4:48:48The layer containing the polymer according to the invention is preferably used as an image-receiving layer in a photographic element in a color diffusion transfer process. be done. This photographic element may be one in which a layer containing the polymer according to the present invention is coated on a support. That is, a layer containing the polymer according to the present invention may be deposited on a support on which a neutralizing layer containing an acid substance and a timing layer are coated in order, or the neutralizing layer and timing layer described above may be coated. Alternatively, a layer containing the polymer according to the present invention may be directly coated on the support.

The polymer of the present invention can be used in the image-receiving layer in combination with other polymer mordants. Any other polymer mordant can be selected from among known ones and used in any proportion within the range that does not inhibit the effects exhibited by the polymer according to the present invention.

The polymers according to the invention can also cure on their own to form a mordanting film, or can be used in combination with another binder, preferably a binder consisting of a water-miscible hydrophilic organic colloid. A film can be formed. Suitable binders include, for example, gelatin, derivative gelatin such as acid-treated gelatin, film-forming compounds such as polyvinylic alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, starch, polyvinyl methyl ether, polyacrylamide, and polyvinyl pyrrolidone. can. It is desirable that the content of the polymer according to the present invention in the image-receiving layer is in the range of 10 to 100% by weight.

The coating thickness of the image-receiving layer containing the polymer according to the present invention can be varied depending on the purpose, and is optimally about 3 to 10 μm. In addition, the image-receiving layer may contain various additives commonly used in photographic technology, such as ultraviolet absorbers and fluorescent whitening agents.

Photographic elements having a support and a layer containing the polymer according to the invention as an image-receiving layer can be used in various conventionally known photographic materials (e.g. photographic materials for color diffusion transfer, dye transfer methods). However, one preferred embodiment is its use as a photographic element in a color diffusion transfer photographic material.

The first preferred photographic material for color diffusion transfer using the photographic element according to the present invention is (1) a first support and an essential layer thereon comprising a polymer represented by the general formula (I) above. (2) a second support and at least one light-sensitive silver halide emulsion layer thereon in combination with a color image-forming substance; .

The second preferred one is: (1) at least one photosensitive silver halide layer combined with a support and an image-receiving layer containing a polymer represented by the above general formula as an essential layer thereon and a color image-forming substance in order; A photographic element having an emulsion layer and (2) a processing sheet that is superposed or capable of being superimposed on the layer furthest from the support of the photographic element.

The photographic elements, photographic materials, and film units for color diffusion transfer according to the present invention may optionally include an acid substance-containing layer (neutralization layer), a neutralization rate adjustment layer (timing layer), a reflector-containing layer, and an opaque layer. A layer containing a curing agent, a release layer, etc. can be used. When the neutralization layer and the timing layer are provided on a support having a layer containing the polymer according to the present invention or a silver halide emulsion layer, the neutralization layer and the timing layer are formed on the support and the layer containing the polymer according to the present invention provided thereon. It is preferable to provide a neutralization layer and a timing layer in this order from the support side between layers containing coalescence or silver halide emulsion layers. Further, when provided on a support body having both a layer containing the polymer according to the present invention and a silver halide emulsion layer, 1-1: On the support body, the layer containing the polymer, and the emulsion layer. It is preferable to provide a neutralizing layer and a timing layer in this order from the support side between them. When the neutralizing layer and the timing layer are provided on the above-mentioned treated sheet, it is preferable to provide the neutralizing layer and the timing layer in this order on the treated sheet. A reflective agent-containing layer and an opaque agent-containing layer are formed on a support having both a layer containing a polymer according to the present invention and a silver halide emulsion layer. It is preferable to provide the curing agent-containing layer and the emulsion layer in this order. The release layer is preferably provided on a support having both a layer containing the polymer according to the present invention and a silver halide emulsion layer, and between the layer containing the polymer and the emulsion layer.

As the color image-forming substance used in combination with the silver halide emulsion layer, various conventionally known materials can be used, whether or not they are substantially diffusive. In particular, the first color image forming substance is the so-called pigmented image side. A dye developer is a compound that has both a dye part or its precursor part and a silver halide developer part in one molecule, and the dye developer as a color image forming substance is oxidized by silver halide. As a result, a change in diffusivity occurs.

A typical second color image-forming material is a so-called diffusible dye-releasing coupler, which undergoes a coupling reaction with a silver halide color developing agent oxidized by a silver halide to release a diffusible dye and its precursor. It is something that is emitted.

A typical third type of color imaging material is a non-diffusible color imaging material that can be oxidized by the oxide of a silver halide developer to release a diffusible dye or its precursor in an alkaline medium. Dye-releasing redox compound, Dy
eReleasing Redox Compound
s, hereinafter referred to as VDRR compound.

A further representative fourth color image-forming material is a non-diffusible dye image-forming material in which the release of diffusible dyes or their precursors is inhibited in alkaline media as a function of the oxides of the silver halide developer. It is something that

When the third color image forming material, that is, the DRR compound, is used, the photosensitive tin halide emulsion layer is exposed to light to form an a image in the photosensitive silver halide emulsion layer, and then Processed with an alkaline processing solution in the presence of a silver halide developer. As a result of the treatment with the alnoalitic treatment liquid, silver halide fj1. Where the oxide of the developer is generated, the oxide of the silver halide developer causes the D
The RR compound is oxidized to release the diffusible dye or its precursor.

Diffuse color released from this DRR compound.

The color image is transferred by diffusion to the image-receiving layer, thereby forming a color image.

Furthermore, when the fourth color image-forming substance is used, the photosensitive silver halide emulsion layer is exposed to light to form a latent image in the photosensitive silver halide emulsion layer, and then the silver halide emulsion layer is exposed to light. Processed with an alkaline processing composition in the presence of a developer.

As a result of the treatment with the alkaline processing liquid, the release of the diffusible dye or its precursor from the non-diffusible color image-forming substance is inhibited in areas where oxides of the silver halide emulsion are produced. - 10,000... In areas where the oxide of the silver oxide developer is not formed, the non-diffusible color image forming substance also acts as a diffusible dye, its precursor is released, and is transferred to the image-receiving layer by diffusion to form a dye image. form.

The polymer according to the present invention represented by the above general formula (I) has good mordanting ability, especially with respect to acidic dyes or their precursors. The precursor of the acidic dye is a sulfonic group,
It has an acidic group such as a carboxy group, an ionizable sulfamoyl group, a hydroxyl group-substituted aromatic hydrocarbon ring group, or a skeletal heterocyclic group.

As mentioned above, various color image-forming substances can be used in the five-true pigment of the present invention, among which are diffusible pigments having a sulfamoyl group that can be ionized as a result of treatment with an alkaline treatment composition, or Preference is given to using color imaging materials that produce precursors, especially DRR compounds.

When the above-mentioned typical color image-forming materials are used, a positive diffusion transfer dye image is produced if development is carried out using a negative-working halogenated emulsion layer. On the other hand, when using the typical second and third color image forming materials mentioned above in C1, a negative diffusion transfer dye image can be obtained by developing with a negative-working silver halogenide emulsion layer. It will be done. Therefore, in order to obtain a positive diffusion transfer dye image using the second method, a reversal method is necessary. For example, surface positive emulsions, ie internal latent image emulsions, as well as fogged emulsions can be used. Further, a layer containing a color image forming substance and physical development nuclei may be provided adjacent to the negative-working silver halide emulsion layer by processing with a developer containing a silver halide solvent. It also contains a compound that reacts with the oxide of the developing agent to release a development inhibitor, such as l-phenyl-5-mercaptotetrazole. A layer containing a reducible metal salt may also be provided. Combinations of these emulsions and color image-forming substances can be used in the present invention, and any method can be selected to provide negative and positive dye images.

The color image-forming substance used in the present invention is usually combined with a silver halide emulsion layer or, preferably, gelatin or polyvinyl alcohol as a carrier of an adjacent layer located on the exposure side with respect to the emulsion layer. It is preferred that the color image-forming material be dispersed in a variable manner depending on the type of color image-forming material in the aqueous protective colloid. The amount of color image-forming material used in the present invention can vary widely depending on the compound used and the desired result, but for example, from about 0.5% to about 10% by weight of the hydrophilic protective colloid coating solution being applied. It is preferable to do so. If the material diffused and transferred to the image-receiving layer is not a dye but a dye precursor such as a leuco dye or a coupler, an oxidizing agent, a color developing agent, or a diazonium compound, etc., is added to the image-receiving layer in order to convert these into dyes. It is preferable to include it in the layer. The image-receiving layer containing these oxidizing agents, color developing agents, diazonium compounds, etc. is disclosed in U.S. Pat.
, No. 798, No. 3,676.124, French Patent 2
, 232, No. 7.76, 2.2:', 2.717
No., JP-A No. 50-80131, etc.

The silver halide emulsion used in the present invention is, for example, a colloidal dispersion of silver bromide, silver bromide, silver chlorobromide, silver iodobromide, bulk bromide, or a mixture thereof. It can consist of

The silver halide emulsion used in the present invention can use an optical sensitizing dye to provide additional photosensitivity. In order to obtain a multicolor image, a blue-sensitive emulsion layer, a blue-sensitive emulsion layer,
It is desirable to sequentially stack a green-sensitive emulsion layer and a red-sensitive emulsion layer, and each emulsion preferably has a yellow image-forming substance, a magenta image-forming substance, and a cyan image-forming substance in combination. In this case, it is preferable to provide an intermediate layer between each combination unit of the color image forming substance and the I/logen emulsion layer. The interlayer prevents undesirable interactions between the emulsion layers and color image-forming material combination units of different color sensitivities, and also controls the diffusivity of diffusible dyes or their precursors and Alcica 1 processing compositions. Make adjustments. As the reflective agent and opacifying agent used in the reflective-side containing layer and the opacifier-containing layer, the same ones as those used in the alkaline processing composition described below can be used. Also, a photographic element according to the invention,
The photographic material can be provided with layers such as a yellow filter layer, an antihalation layer, and a protective layer, if necessary.

The neutralization layer that can be used in the present invention is an acid substance (
Any material may be used as long as it contains a neutralizing agent (neutralizing agent) and lowers the pH within the system after development processing. The material used for the neutralizing agent and (-) is preferably a film-forming polymeric acid having one or more carboxyl groups, sulfonic groups, or groups capable of forming carboxyl groups upon hydrolysis. Any polymeric acid can be used. The aforementioned tying layer serves to delay the pH drop until after the required development and transfer has taken place, i.e., silver halide development and diffusion. Before the transfer image is formed, the neutralization layer prevents an undesirable decrease in the density of the transfer image due to a rapid decrease in the pH within the system.

The support or treated sheet according to the present invention is preferably a planar material C that does not undergo significant dimensional changes during the treatment due to the treatment agent.

The support is used for the purpose of anti-reflection during exposure or viewing of an image, as disclosed in U.S. Pat.
An antireflection layer may be provided as described in US Pat. No. 4,040,830, or a non-planar surface may be provided as described in US Pat. No. 4,040,830.

The developer permeable layers such as the silver halide emulsion layer, layer containing a color image forming substance, layer containing a reflective agent, layer containing an opacifying agent, and protective layer used in the present invention preferably have a hydrophilic polymer as a binder. [2〈desirably contains gelatin.

As the processing solution used in the present invention, any liquid composition can be used as long as it contains processing components necessary for developing the silver halogenide emulsion and forming a diffusion transfer image. As the solvent for this treatment component, any hydrophilic solvent such as water, methanol, methylcellosolve, etc. can be used. The processing solution should contain a sufficient amount of alkaline agent to maintain the pH necessary for development of the emulsion layer and to neutralize acids generated during the development and color image formation processes. desirable.

In the present invention, it is desirable to provide a layer containing a light-reflecting substance in order to form a white background for the image formed on the image-receiving layer. Suitable light-reflecting substances include titanium dioxide, barium sulfate, zinc oxide, barium alumina stearate, calcium carbonate, 7-silicate, zirconium oxide, kaolin, magnesium oxide, etc., which may be used alone or in combination. Can be used.

The above-mentioned silver halide emulsion, spectral sensitizing dye, neutralization layer,
Conventionally known techniques can be applied to the timing layer, support, binder, curing agent, developer or reflective material. For more details, see the above-mentioned Special Publication No. 57-24537.
listed in the number.

In the above, the case where the polymer represented by the general formula <I) according to the present invention is mainly used as a mordant in the image receiving layer in the color diffusion transfer method has been explained. Diffusible dyes or their precursors or impurities may diffuse into the image-receiving layer to increase the minimum density of the transferred image or may be used as scavengers to prevent staining altogether. As a scavenger, the general formula (I
) When used, its addition location is preferably in the photographic material in a layer located on the opposite side of the image-receiving layer with respect to the silver halide emulsion layer during processing, or between the silver halide emulsion layer and the image-receiving layer. Depending on the layer structure, there are various layers such as a timing layer, an intermediate layer, and a protective layer, but there are also other layers, such as those between a timing layer and a neutralization layer, an opacifying agent-containing layer, and a halogen layer. A scavenger layer containing the polymer may be provided between the silver emulsion layers. When the polymer is used as a scavenger,
The mordant in the image-receiving layer may be a polymer according to the invention or another polymer. When using the polymer according to the present invention as a scavenger, the amount to be added is from 0.2v to 3.0v when it is added to a layer located on the opposite side of the halogenated emulsion layer from the image-receiving layer as described above. fi'/m is preferable, and when it is added to a layer located between a silver halide emulsion layer and an image-receiving layer, 2Q my to 16o and wv/nj are preferable.

The polymer according to the present invention is not limited to the color diffusion transfer method, but can also be used in dye transfer methods such as the wash-off relief method and the dye transfer method. That is, good Dye 1IiII images can be obtained by transferring dyes from a dye transfer matrix onto a photographic element comprising a layer containing a polymer according to the invention and a support.

The dye used in the dye transfer method is Pontayl green SN Ex.
Exp color index 737), tartrazine (
Tartrazine; color index 640)
, Acid Magenta 0 (Ac1d Magenta
01 color index 692). Furthermore, the polymers according to the invention can also be used in optical filter layers, such as U.S. Pat. No. 3,282.

They can also be used in antihalation layers such as those described in No. 699. This light filter layer preferably contains a polymer according to the invention, a filter dye mordanted on the polymer and a hydrophilic binder.

The present invention will be specifically explained below with reference to synthesis examples and examples, but the present invention is not limited thereto.

Synthesis example 1. Synthesis of N-vinylbenzylimidazole 11 In a flask, add 140 Imidazole and 300 methanol.
Add 109 g of m1 sodium methylate and stir to dissolve. The liquid temperature is raised to 70°C and methanol is distilled off under reduced pressure. When the solid precipitates and becomes a slurry, 450 ml of dimethyl formaldehyde is injected and distilled again under reduced pressure. After methanol has finished distilling, the reaction solution is heated to 35°C.
300 g of chloromethylstyrene was added dropwise. At this time, the liquid temperature is maintained between 35 and 40°C.

After completion of the dropwise addition, the mixture was stirred at 40°C for 3 hours. After cooling to room temperature, add toluene IA and wash 4 times with 17 water, then 2
N hydrochloric acid 1.2A! The monomer is extracted into the aqueous layer. The aqueous layer is added dropwise to ice-cooled 1,5N sodium hydroxide solution 21. Extract the precipitated oil layer with 1.21 g of dichloromethane. After washing with water, it is dried over magnesium sulfate and concentrated to obtain the desired product. Yield 306.4g (yield 85%)
Purity 78% Synthesis Example 26 Synthesis of Exemplified Polymer 1 Stirring device, cooling tube, thermometer, nitrogen gas introduction bone (D21
'Pour 100 g of the monomer obtained in Synthesis Example 1 and 1.25 g of degassed water into a fourth flask and stir. Trunks H- here
45 (sodium salt of sulfated product of alkylphenol and ethylene oxide condensate, NOF O'Jl)
) Insert 40.0 m. Next, styrene 20.6,
9. Add 7.8 y of divinylbenzene and stir at room temperature for the addition period. Thereafter, the temperature is raised, and when the liquid temperature reaches 65° C., an initiator solution prepared by dissolving potassium hydroxide 12,9 and azobiscyanovaleric acid x, sg is added dropwise to 3 Bml of degassed water. Continue stirring at 65°C for 3 hours. After cooling to room temperature, it was filtered to obtain a polymer latex. 143
0 ml (solid content 30.0%) Example 1 Exemplary compound II/11. ．． 2.4.8. was synthesized according to Synthesis Example kt.

On the other hand, as comparative compounds, the following compounds were used in JP-A-55-2
Synthesized according to No. 2766 and JP-A No. 55-48210.

'Formula%Formula%() Exemplary Compound 1. , 2.4 , 8. and comparative compounds (
a), (8g each of bl, 4-hydroxymethyl-
4-Methyl-1-phenyl-3-pyrazolidinone 0.9
8.9, gelatin 8y1 mucochloric acid 0.6,9,1
0% emulgen-108 (,j-'!j-oki/ethylene nonylphenyl ether, Kao 7)5su'M) 0.75
Add water to 1rIJ.

Dissolve so that the finished amount is 250 d, and the coating prohibition is 2-7 g/lr? , 4-hydroxymethyl-4-
Methyl-1-phenyl-3-pyrazolidinone 0.33I
The film was coated on a clear polyethylene terephthalate support having a thickness of 100 μm so as to give an image-receiving layer (first layer).

The following second layer is added to the first layer such as the above-mentioned image receiving layer and comparative image receiving layer.
The layers were coated to form image-receiving sheets 1, 2, 4, 8 degrees a and b, respectively.

Second layer Protective layer of gelatin (0,6511/rrt ) and glyoxal (o, o 69/rrl ).

Next, the following layers were sequentially coated on a transparent polyethylene terephthalate film support with a thickness of 180 μm to prepare a photosensitive sheet 1. Ta.

No. 17+-1" F magenta dye i!
rt).

[■]

2nd layer Green-sensitized negative type silver halide emulsion layer Green sensitized negative type silver halide emulsion (silver coating amount 05g β included 2-
Potassium occudenlehydroginone-5-sulfonate (o, 1711/rrl) and gelatin, (1,3
1/1rt) green-sensitive I/silver halide emulsion layer.

3rd layer: layer containing gelatin (0,94 &/go).

The photosensitive sheet described above was exposed stepwise using wedges having different densities.

1121418. is then immersed for another second at a temperature of 32° C. and 32° C. in an activator solution of the following composition housed in a shallow tray-type processor and then passed between a pair of pressure rollers. Superimposed on a and b.

Composition of activator solution Potassium hydroxide 56.2. ji' 5-Methylbenzotriazole 7.2911-Aminoundecanoic acid 2, Oy Potassium bromide 2.0g Finish to 1000 cc with water.

After 2 minutes, the photosensitive sheet and the image receiving sheet were peeled off, and the image receiving sheet was neutralized with an acetic acid aqueous solution, and then the reflection density was measured (using a Sakura photodensitometer PDA-60 (manufactured by Konishiroku Photo Industry)).
was measured using a green filter.

After peeling, a part of each specimen was masked with black paper to block light as a photostability test sample, and the remaining part was
exposed. Next, this test piece was exposed to a sample surface illuminance of 60.0.
It was irradiated for 72 hours at 00 lux.

Ratio of density between masking area Dm and non-masking area with density near 1.0 D/Dm X 100 (%) (ρD
), the following results were obtained.

"l"1 I<Water For example, 8-1 above means a combination of the image-receiving sheet 8 and the photosensitive sheet 1. Same goes for the others.

The above results show that, compared to quaternary salt mordants, imidazole group-containing mordants exhibit superior performance in terms of the photostability of dyes, and the imidazole copolymer of the present invention has excellent coating properties. There is no change in dyeing strength due to hardening agents, etc., and it exhibits excellent mordanting properties and has excellent image stability.

Example 2 Photosensitive sheet 2 was prepared by sequentially coating the following layers on a transparent poly(ethylene terephthalate) film support having a thickness of 180 μm.

+1) Methanol solution containing 100 parts of acid polymer of neutralization layer poly(n-butyl acrylate tocoacrylic acid) (weight ratio 30/70) and 2 parts of silane coupling agent (manufactured by Toshi Silicone) as a hardening agent. The coating amount of polymer is IOg/m”
A mesophase layer applied using the extremision method so that

(2) Timing layer prepared by hydrolyzing vinyl acetate-maleic anhydride copolymer, lactonizing, and partially esterifying with n-butanol and having an fC acid/butyl ester ratio of 15785. Lacto7ho+)-r-95 parts and poly(i4
(weight ratio 65/3015) A mixture with 5 parts of chloride (co-acrylic order-co-methyl acrylate) (weight ratio 65/3015) was extracted from an acetate/solution so that the coating grade of the polymer was 3.0 g/m'. l/-timing layer applied by the Schiff/method.

(3) Cyan coloring material layer Cyan image-providing material having the following structural formula (0.64 g/
), tricresyl phosphate (0,329/lr?), tricresyl phosphate (0,329/lr?
) and gelatin (1.6 g/l) and a cyan colored layer consisting of 1.6 g/l.

(4) Red-sensitive negative-working silver halide emulsion layer Red-sensitized negative-working silver halide emulsion (silver coating amount 0.35 g/rr
l), 2--14G-octadecylhydroquinone-
A red-sensitive negative-working silver halide emulsion layer consisting of potassium 5-sulfonate (0,17&/rrt) and gelatin (0,15Fl/rl).

(5) Intermediate layer gelatin (0,6311/rrl) and 2-acetyl-
5-J4G-octadecylhydroquinone (0,459
/d).

(6) Magenta coloring material layer A magenta image-providing substance (0,8
1 part m), diethyl laurylamide (0,4,j)
/lrl) j? and gelatin (1.5g/i)
A 4-zenta color material layer having

(7) Green-sensitive negative-working silver halide emulsion layer Green-sensitized negative-working silver halide emulsion (@coating It O, 5 g/m )
Potassium 2-octadecylhydroquinone-5-sulfonate (,0,179777L') and gelatin (1
, 311 parts m).

(8) Intermediate layer gelatin (0,63y/mj) and 2-acetyl-5-
zzG-octadecylhydroquinone (0,451!/
(9) Yellow colorant layer Yellow image-providing material of the following structural formula (0,569/m'
), tricresyl phosphate (0,25&/rrt)
A yellow coloring material layer consisting of S and gelatin (0.12 g/lri).

0q N-sensitive negative type halide emulsion layer Blue sensitized negative type silver halide emulsion (silver coating amount 0.551/rrl
), potassium 2-octadecylhydroquinone-5-sulfonate (0,17117m) and gelatin (13F
! /rrl) Blue-sensitive silver halide emulsion layer.

■ Protective layer gelatin (0.8i/nX), methacrylate beads (2-4μm, 15g/m) particle size 0.2μ
7 Lika of m (0,4511/vt) i- and tetrakis(vinylsulfonylmethyl)methane (0,211/vt)
rrt).

The photosensitive sheet 2 was exposed stepwise using wedges having different densities.

The image-receiving sheet of Example Carp 1 was treated with 1% 2*41za and b, and the photosensitive sheet 2 exposed to light using the treatment solution.

After 5 minutes, the photosensitive sheet and the image-receiving sheet were peeled off, and the cross-radiance density (using a Sakura photoelectric densitometer PDA-60, manufactured by Konishiroku Photo Industry ■) was measured at (λmax = 644 nm).
), green (λmix = 546 nm), blue (λzn
ax = 434 nm), and the following results were obtained.

In Table 2, for example, 8-2 above means a combination of the image-receiving sheet 8 and the photosensitive sheet 2. Same goes for the others.

A photostability test was conducted under roughly the same conditions as in Example 1.

Table 3 As is clear from Table 3.4, when the photographic element of the present invention is used, it generally has a high mordant power, a high Dmax, and good color image retention, especially the problem of magenta. It has excellent photostability.

Example 3 The back of the multi-Jft1 photosensitive sort 2 produced in Example 2,
A multilayer photosensitive sheet 3 was prepared by replacing the 4th, 7th, and 10th silver halide emulsion layers with the following silver halide emulsions.

(4) Red-sensitive internal image type direct reversal silver bromide emulsion (scissors coating) The purpose of the present invention is fully achieved, it provides good properties as an image-receiving layer in the color diffusion transfer method, and is also good as a scavenger. It opened up a field of mordants that are widely applied.

Agent Yoshimi Kuwahara

Claims (1)

Claims: A photographic element comprising a layer containing a unit represented by the following general formula (I) and a substantially water-dispersible polymer. General formula (I) R. [In the formula, A is a coelectrically capable monomer unit having at least two ethylenically unsaturated groups, B is a copolymerizable α, β-
It is a unit of ethylenically unsaturated monomer. R2 is a methyl group spanning hydrogen atoms, R and Rs are hydrogen atoms, an alkyl group, or an aryl group. L is a divalent linking group. Also, z, y and J, 0.5≦χ≦6.0.0≦y≦7
9.5.20≦2≦99.5 and represents the copolymerization mol%. ]