JPS6028650A - Photographic element - Google Patents

Abstract

PURPOSE:To obtain an image receiving layer having high mordant effect by providing a layer comprising a specified polymer. CONSTITUTION:The photographic element of this invention comprises a layer contg. a polymer expressed by the general formula( I ). In the formula, A is a unit of copolymerisable monomer having at least two ethylenic unsatd. groups. B is a unit of copolymerisable alpha, beta-ethylenic unsatd. monomer, R1 is H or methyl; R2, R3 and R4 are alkyl groups; R5 and R6 are H, alkyl or aryl group; L1 and L2 are divalent joint groups, and X is a univalent anion; p, q, r, and s are mol% of copolymerised portion, where 6.0>=p>=0.80>=q>=r>10.90>=s>=10. Specific examples for useful monomer B are alkenes, alkapolyenes, styrenes, monoethylenic unsatd. esters of fatty acids, etc.

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION This invention relates to photographic elements containing layers containing novel polymers, and in particular to photographic elements for color diffusion transfer in which the polymers are used as good mordants for dyeing. (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. A combination of photographic elements,
Alternatively, in a light-sensitive element, a photosensitive layer containing a silver halide J' emulsion is imagewise exposed to form a latent image, which is developed with a processing solution, and at the same time the color image-forming substance is exposed in an imagewise manner. forming a color image material. At least a portion of this color image material diffuses and is transferred to an image receiving layer in an image receiving element provided overlying the emulsion layer, thereby transferring dye image 1? ! form. It is known to use various polymeric dyes as mordants in the image-receiving layer in order to prevent migration of the dye. This polymer, ) > 4, f'l includes, for example, U.S. Pat.
As described in No. 1,439, quaternary nitrogen raw material l
Polymers having imidazole groups at 5° C. are known, for example, as described in British Patent No. 2,011,912. However, these polymers do not seem to have sufficient properties h1:. In other words, the dye retaining ability of this type of combination used in the image-receiving layer with a mordant ([2] is weak, and dye migration occurs, resulting in a decrease in the color density of the obtained dye image (and not only the color balance but also the brightness). In addition, the ability to efficiently and quickly mordant the color image materials that diffuse during the development process is insufficient, resulting in poor images with poor sharpness and sharpness, and contaminants generated after the development process are insufficient. It is susceptible to contamination, and the mordant itself turns yellow when exposed to natural light for long periods of time.On the other hand, even compounds that meet these conditions have poor film-forming ability or have a negative effect on photographic performance. There have been problems such as the release of substances that cause Power of Inclusion as a Mordant 2 - Regarding photographic elements in the diffusion transfer process, the first object is to provide a photographic element having an image-receiving layer with excellent mordanting ability. It is an object of the present invention 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 time. It is an object of the present invention to provide a photographic element having a raw image layer which prevents the dye image formed in the image-receiving layer by development processing from deteriorating due to movement of the dye or from deterioration due to contaminants, etc., and has good image storage stability. A fifth object of the present invention is to provide a photographic element containing a polymer having excellent mordanting ability without adversely affecting photographic performance. Membrane type tJV, which is excellent and also excellent when used with a binder, (-
The purpose is to provide C11 with a sample containing a polymer used as a mordant. (55) Decay of the Moon) 1) The purpose of Akinoga is to create a copy characterized by having a layer containing 'i11 itself as shown in the following general formula (I)!゛” Achieved by Yasui. -fci formula (1) 11. + is hydrogen atom J or methyl group, 几2
and 1 (11 is an argyl group and may have a substituent, and the total number of carbon atoms is preferably 1 to 4. J represents an alkyl group or an aryl group and has a substituent) The alkyl group preferably has 1 to 16 carbon atoms, and the aryl group preferably has 7 to 12 carbon atoms.Also, ya and uma represent a hydrogen atom, an alkyl group, or an aryl group,
It may have a substituent, and the alkyl group preferably has 1 to 4 carbon atoms. The total number of carbon atoms in each horse is preferably 1 to 12. Also, the R
5 + 几. The total number of carbon atoms in the aryl group represented by is 6 to 12
is preferable. It represents an anion, preferably a halogen ion or an alkyl sulfate ion. Ll is a divalent linking group, and is an acid amide group or an ester group, and is preferably an acid amide group, particularly a carbonylamino group. L2 is also a divalent linking group, and preferably, in the lower divalent linking group L2', "2' to -L-L-, L is the imidazole side linking group 2 2 2 group. L is an arylene group, an acid amide group or an ester group, and L< is a phenylene group,
carpol amino group or carbonyloxyno, (8. 1 and 1 are alkylene group, arylene group,
j+, +i' substituted V. The total number of carbon atoms is 1 to 4 for the gylene group, and 7 for the arylene group.
12. When it is an alkylene arylene group, it is preferably 7 to 12. In addition, 14.4) the ammonia salt moiety is 1
In ~, the position bonded to the ben I electron/ring is preferably the m-position or the P-position due to the bonding of the divalent linking group 1, and the bonding position of the divalent linking group 1 is preferably the m-position or the P-position. )・The effect of. Imidazole: The bonding position of J1℃ and 1 is the imidazole salt's 1's ('+>p'i,j', [2 but!
1" and the 1st position is more feminine. 4 having at least two ethylenically unsaturated groups as described above
, ", 3ti combination HJ'fif' jX is preferably a monomer represented by the following general formula (11). % where KIL is an integer greater than 2, preferably 2
where 几 is independently selected from a hydrogen atom and a methyl group; -CON
H=-8O2N)←, I, and furthermore, linking groups combining various groups [e.g. methyleneoxycarbonyl, ethylenebis(oxycarbonyl), phenylenebis(oxycarbonyl), 4,4'-ia furohiritenpis(phenylene) oxycarbonyl), 1,2,3-propanetriyltris(oxycarbonyl), cyclohexylenebis(methyleneoxycarbonyl), methyleneoxymethylenecarbonyloxy, methyleneiminocarbonyl, oxymethyleneoxy, ethylenebis(oxyethyleneoxycarbonyl) , ethylidentris (oxycarbonyl)]. It is represented by general formula [11]. Suitable j:r, (<If) as the t+i, ia form include divinylbenzene, allyl acrylate-1, N-allyl methacrylamide, 4,41-isopropylidene diphenyl diacrylate, 1,3-butylene dimethyl cucrylate, 1.4-
Cyclohexylene dimethylene dimecacrylate, diethylene glycol dimethacrylate, divinyloxymethane, ethylene diacrylate, ethylidene dimecacrylate, 1,6-diacrylamide, N,N-menalene bisacrylamide neopentyl dimecacrylate, Phenylethylene dimethacrylate-I, 1 triethylene glycol dimethacrylate, 1 triethylene dimethacrylate, 2.2.2-tric

[ ] Ethylidene dimethacrylate, triethylene glycol dimethacrylate, ethylidene trimecrylate 1, gloviridine triacrylate, beer aryrogine acetate, vinyl methacrylate), I-vinyrogine 7-2-allyloquinethane) can. Also preferred for fi) is divinylbenzene. Examples of α,β-eglenic unsaturated J1+ that can be combined with the above-mentioned groups include alkenes (1' such as ethylene, propylene, ■-butene, /f-7-one, 2-
methylpentene, ), alkapolyene (e.g. 1.1
．． 4.4-tetramethylbucudiene, inzolene), styrene a (Nt-styrene, α-methylstyrene, P-
chlorstyrene, p-methylstyrene, m-ethylstyrene), monoethylenically unsaturated esters of 11Fr fatty acids (e.g. vinyl acetate, allyl acetate), esters of ethylenically unsaturated mono- or dicarboxylic acids (e.g. methyl mecrylate) lower alkyl esters of methacrylic acid, acrylic acid such as butyl acrylate)
(low i furkyl ester, diethyl, styrene malonate), halogenated olefins such as vinylidene chloride, dienes such as butadiene, nitrile forces such as acrylonitrile, acrylamide forces such as acrylamide, methacrylamide, diacetone acrylamide ■ 1. Vinyl ethers such as vinyl ethyl ether, vinylpyrrolidone, etc. (g:p2==CF2,
Examples include fluorinated vinyl compounds such as Chino-ni. Among these, preferred are styrenes and esters of ethylenic monocarboxylic acids. In the general formula (I), P, q, r and 3 each represent 1
1j jA small unit copolymerized morch, 6.0≧P
≧0 80≧9≧0 90≧r≧10 90≧t≧1O -Q 'X, ys, r and 5 are preferably 70≧r≧
25 70≧5≧25. Furthermore, the monomers represented by A, B and K in the general formula (I) K may each contain two or more monomers within the range defined by p, q, r and S, respectively. It may contain units. In the present invention, it is particularly preferred that the polymer is a substantially ash-dispersible polymer. The quaternary ammonium salt-containing polymer of the present invention can be produced by polymerizing or reacting with the corresponding quaternary sand ≠ 44 to form a quaternary ammonium salt, as shown below. It can be synthesized by polymerizing a precursor monomer and then producing a quaternary ammonium salt through a polymer reaction. The molecular weight of the polymer of the present invention is arbitrary, but a low molecular weight is unfavorable in terms of mordant ability or dye fixing ability, and conversely, a high molecular weight is unfavorable in terms of film forming ability or coating properties, so it is about 5,000 yen. or about 1,000,000
Preferably between 0 and even about 10,000 to about 5
00,000 gives good results. In producing a water-dispersible polymer containing a quaternary ammonium salt such as the polymer according to the present invention, for example, a monomer having a halogenated alkyl group as described in U.S. Pat. No. 3,958,995 is used. 1d and (t, β-
Method 6 of emulsion polymerizing a monomer having an ethylenically unsaturated group and then reacting it with a tertiary amine; and a monomer having a Kl tertiary amine instead of the monomer having a halogenated alkyl group. Is there a well-known method in which a quaternizing agent is reacted after emulsion polymerization using the former method? This is undesirable because it may cause problems or have an adverse effect on photographic quality f11:. UnjPi 1jll K l system Ru71j is combined using the latter method, which is advantageous in terms of photographic performance! It is a very suitable polymer for making IIIJ. Polymeric mordants containing quaternary ammonium salts are 11!
As described in Japanese Patent Publication No. 55-22766, it has excellent mordant ability, but has a Hi point that is inferior in terms of image retention, especially light resistance.On the other hand, η・merging k111, dye containing a heterocyclic compound is described in British Patent No. 2,011,91
As described in No. 2, etc., it has excellent light resistance. In order to satisfy both the mordant ability of the quaternary ammonium salt and the excellent light resistance ability of the imidazole group, an image-receiving layer was formed by mixing a quaternary ammonium salt polymer and an imidazole polymer. Only one of the characteristics could be satisfied; it was not possible to satisfy both characteristics at the same time. However, by copolymerizing a monomer having a quaternary ammonium salt precursor and a monomer having an imidazole group, it has become possible to obtain a polymer mordant that satisfies both properties. Next, typical examples of the polymer of the present invention will be listed, but the present invention is not limited thereto. (Exemplary polymer) In the monomer containing an imidazole group, when the imidazole group is directly or indirectly linked to a phenylene group, it may be a mixture of the m- and p-position bonds of the phenylene group (
・. The polymers of the present invention can be used, for example, in U.S. Pat. No. 3,183,219
No. 3,330,656, No. 3,253,921, Special Publication No. 47-560, Journal
of Applied polymer 5science
) Vol. 9, p. 903 (1965) Vol. 10, No. 14
62 pages (1971) Preparative Methods of Polymer Chemistry by W. R. Sorenson and T. W. Campbell
(olymerChemistry) (John W.
iley & 5ons Inc., New York.
1961) Research Conflict Distroger (&5CRC
It can be easily synthesized by arbitrarily adopting a polymerization method and reaction conditions such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization according to the method described in No. 14103 and the like. The layer containing the polymer according to the invention is preferably used as an image-receiving layer in a photographic fabric in a color diffusion transfer method. This photographic element may be one in which a layer containing a polymer according to the present invention is coated on a support. Zubu Z straw, neutralization layer containing acid substance and timing j?・JllI′i for 1
Itc #7, . 11-
+B) A layer containing a smudge may be coated or the neutralization IF described above may be coated.
The layer containing the m-coalescence according to the present invention may be directly coated on the support without coating the ii6 and timing layers. "5A light m combination can be used for image reception/?・1 in combination with other polymer mordants.Other polymer mordants J'
Ill trotJ-2 can be selected and used in any ratio from among those known in the art, as long as they do not inhibit the effects of illI itself according to the present invention. m coalescence also cures itself and becomes medium 11'!
It can form a film and other binders (
11♂' can also be used as a mordant when used in combination with a binder consisting of a hydrophilic organic colloid that is miscible with Dj water! wo can be formed. Binding with a suitable binder or forming a film of gelatin, acid-treated gelatin, etc.; Examples include chemical compounds. It is desirable that the content of the polymer according to the present invention in the image-receiving layer is in the range of 10-1004 by weight. The coating JFI 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. The photographic element having the support and the m-coalescence layer according to the present invention as an image-receiving layer can be any of various conventionally known photographic materials (for example, color diffusion transfer R1 material, dye transfer dyeing method).
One preferred example is a color diffusion transfer photor! , when used as a photographic element in U-materials. The first preferable 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 containing a polymer represented by the general formula CDIC. (2) a second support and at least one light-sensitive halogenated layer associated thereon with a color image-forming material; 'IJ
, consisting of a photographic element having an emulsion layer. The second thing that is more desirable is (1) a support and an image-receiving layer and a color image f/H containing a polymer represented by the above general formula in order as an essential layer on the support:
At least one layer of sensitizer combined with a forming substance 1. A photographic material having a transparent silver halide emulsion layer; C1; 1. A photographic element for color diffusion transfer according to the present invention 1c, a photographic rt,
t1 year old 1t6'' and acid as needed in the film unit! Val"+ containing layer (neutralizing layer), neutralization rate adjusting layer (timing II"i), reflective side containing layer, opacifying agent containing layer, ) 11f tN (9 can be used for 1 layer. Medium When the sum 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 described above, the layer and the timing layer are formed on the support and 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 the silver halide emulsion layer or the silver halide emulsion layer. In addition, when provided on a support having both a layer containing the polymer according to the present invention and a silver p-genide emulsion layer, the layer containing the polymer and the aging agent layer are provided on the support and the layer containing the polymer and the aging agent layer. It is preferable to provide a neutralizing layer and a timing layer in this order from the support side between them. Further, when a neutralizing layer and a 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. The reflective side-containing layer and the opacifying agent-containing layer are a layer containing the polymer on a support having both a layer containing the polymer according to the present invention and a silver emulsion layer, a reflective side-containing layer, It is preferable to provide the opacifying agent-containing layer and the emulsion layer in this order. t'l The Kf layer may be provided between the layer containing the polymer and the emulsion layer on a support having both the layer containing the polymer according to the present invention and the silver norogenide emulsion layer. . Color ri used in combination with silver halide emulsion layer
As the rii f quadrate acid substances, each of the conventionally known
A typical Pr(- color image forming substance is a so-called dye developer. A dye developer contains a dye moiety or its ii in one molecule.
l, the sound body part and the silver halide developer part are combined.I!
A compound having color image 1' with silver halide
7゛When the dye developer as a forming substance is oxidized, il
, which causes a change in diffusivity. Typical second color imaging materials are so-called diffusion +-1=
The dye-releasing coupler releases a diffusible dye or its precursor by a coupling reaction with a silver halide color developing agent oxidized by silver halide. Form 5ν; The third color image-forming material is a non-diffusive color image f.
If q' forms '1'ηff't and is converted into an oxide of a silver halide developer, it becomes a diffusible dye in an alkaline medium and can release its precursor (dye-releasing property). 1./Dox compound, IJye Relea
sing &doxCompound (hereinafter referred to as 几It compound). A further representative fourth color image forming material η is a non-diffusible dye image-forming substance which is a dye or its precursor which is diffusible in the alkali IJ tl medium as a function of the oxide of the silver halogenide developer. release is inhibited. When the third color image-forming substance, i.e., compound I) RIt, is used, a latent image is formed in the photosensitive silver halide emulsion layer by exposing the photosensitive silver halide emulsion layer to light. and then processed with an alkaline processing solution in the presence of a silver halide developer. As a result of the treatment with the above-mentioned alkaline processing liquid, the oxide of the silver halogenide developer is generated, and the oxide of the silver halogenide developer causes
Above 1) 11. When the compound is oxidized, l' releases the diffusible dye or its precursor. D) The diffusible dye or precursor released from the compound is transferred to the image-receiving layer by diffusion to form a color image. When the photosensitive silver halide emulsion layer is exposed to light,
A latent image is formed in the photosensitive silver halide emulsion layer,
It is then processed with an alkaline processing composition in the presence of a silver halide developer. As a result of the treatment with the alkaline processing liquid, in areas where oxides of the silver halide emulsion are produced, the release of the above ii+, 11 diffusive color image-forming substances and the diffusible dye or its precursor is inhibited. On the other hand, in areas where the oxide of the silver halide developer is not produced, the diffusible dye or its precursor is released from the non-diffusible color image forming substance,
The polymer according to the present invention, which is represented by the above-mentioned receptor r"3 (transferred to the layer and gives impression of the dye image by diffusion. The acidic dye or its precursor has a Z mordant ability.
, an acidic group such as a hydrocarbon ring group or a heterocyclic group. /+:'';6 Various color image-forming substances can be used in the photocopying material according to 6. Among them, sulfamoyl groups that can be ionized as a result of treatment with an alkaline processing composition are used. It is preferable to use a color image-forming substance that produces a diffusible dye or its precursor having Development using silver emulsion R1 provides a positive diffusion transfer dye image.On the other hand, when the typical second and third color image forming materials mentioned above are used, a negative tone image is obtained. If development is carried out using a silver halide emulsion layer, a negative diffusion transfer dye image can be obtained.Therefore, in order to obtain a positive diffusion transfer dye image using the second method, a reverse method is required. For example, direct positive working emulsions, i.e. internal latent image type emulsions as well as coupled type emulsions can be used.Also, adjacent to the negative working silver halide emulsion layer, color image forming substances and physical development nuclei can be used. A layer containing 1-phenyl-5-mercaptodetrazole may be formed by treating with a developer containing a silver halide solvent. A layer containing a one-color image-forming substance and a spontaneously reducible metal salt may be provided adjacent to the negative-working silver halide emulsion layer containing the agent-releasing compound. A combination of these emulsions and a dye image-forming substance can be used, and a method for producing negative and positive dye images can be arbitrarily selected. , usually a l+l aqueous carrier a-6 such as gelatin, polyvinyl alcohol, etc., which is the carrier of the silver halide emulsion layer to be combined or, preferably, the adjacent layer located on the exposure side with respect to the emulsion layer.
It is preferred to disperse the color image-forming material in a specific manner in the colloid depending on the type. The amount of color imaging material used in the present invention can vary widely depending on the substance used and the desired results, but for example, the amount of the applied hydrophilic protective colloid may range from about 0.5 to about 10% by weight. It is preferable to use If the material that is diffusely transferred to the image-receiving layer is not a dye but a dye precursor such as a leuco dye or Kab2-, an oxidizing agent, a color developing agent, a diazonium compound, etc. may be used to convert the dye into a dye. It is preferable that the image-receiving layer contains the following. The image-receiving layer containing these oxidizing agents, color developing agents, diazonium compounds, etc. is disclosed in U.S. Pat.
698,798, French Patent No. 3.676.124, French Patent No. 2,232,776, French Patent No. 2.232,777,
It is described in JP-A No. 50-80131 and the like. The silver halide emulsion used in the present invention may be composed of, for example, a colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof. The silver halide emulsions used in the present invention can use optical sensitizing dyes to provide additional photosensitivity. In order to obtain a multicolor image, it is desirable to sequentially stack a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer from the exposed side, and combine with each emulsion to form a yellow image-forming substance and a magenta image-forming substance. It is desirable to have a cyan image-forming substance. In this case, it is preferable to provide an intermediate layer between each combination unit of the color image forming substance and the halide steel emulsion layer. The intermediate layer is a combination unit of emulsion layers with different color sensitivities and color image forming substances.
In addition to preventing undesirable interactions, it also adjusts the diffusivity of a spreading dye or its precursor or an alkali treatment (111 composition). As the reflecting agent and opacifying agent used in the photographic element according to the present invention, the same ones as those used in the alkaline processing composition described below can be used. can be provided with layers such as a yellow filter layer, an antihalation layer, and a protective layer according to necessity.
'! Any material that contains p)l'a4 lit; l'a4 lit; l'a4 lit; l may be used as long as it contains l'i (neutralizing agent) and can be used in the system after development processing. Used as a neutralizing agent, A2(') is a 1(hard carboxyl!.'-), a sulfonic group, or a carboxyl 7; Any such polymeric acid can be used.The aforementioned timing layer serves to retard the pH drop after the required development and transfer has taken place. Before the development of the silver halide and the formation of the diffusion transferred image, a neutralizing layer prevents an undesirable decrease in the density of the transferred image due to a rapid decrease in the pH in the system. The support or processing note according to the present invention is preferably a planar material that does not undergo a significant change in magnification during processing due to the processing agent. 3,7 9 3,0 2 2 -b
A reflective anti-city layer may be provided as described in U.S. Pat. No. 4,047,804, or the surface may be made non-planar as described in U.S. Pat. The silver halide emulsion layer, the scrap containing the color image-forming substance, the reflective agent-containing layer, the opacifying agent-containing layer, and the developer-repellent layer such as the protective layer used in the present invention contain a hydrophilic polymer as a binder. Preferably, it contains gelatin. The development processing solution used in the present invention includes silver halide emulsion;
Lilyjj1. It is also possible to use a liquid composition that contains the processing components necessary for forming a diffusion transfer image. As a solvent for this treatment component, No. 1
Spicy 1 water 1' such as lily, meknol, methylcellosolve, etc.
1 θ 111 can be used as fl [at will. In the JIII process, emulsion layer glue 1 (p necessary for raising the image)
] 1~, υ^^Contains an alkaline agent capable of removing the acids generated during the various processes of image and color image formation.9 (preferably.A. In I11i Ming, uke@)tl. The white background of the image formed? It is preferable to include a light-reflecting substance to form the TI. Surface (11,!・Barium stearate, carbonate, /ligate, zirconium oxide, kaolin, magui oxide/uno・pj can be mentioned, and these are unique to Jl'l (:l, 41
They can be used together. Below, 1″ silver halogen emulsion, spectral sensitizing dye, neutralized IN, ink layer, support, binder, curing agent,
Conventionally known techniques can be applied to the developer or reflective material. More specifically, the above-mentioned Special Publick Publication No. 57-2
No. 4537. The above has explained the case where the polymer represented by the above general formula according to the present invention is mainly used as a mordant in the image-receiving layer in a color diffusion transfer method. Alternatively, the transferred image may be minimized due to the diffusion of the vIJ precursor or impurities into the image-receiving layer. Nails shown in the above general formula as scavengers. When coalescence is used, the addition location is preferably in the photographic phase material, in a layer on the opposite side of the image-receiving layer with respect to the silver halide emulsion layer during processing, or between the image-receiving layer and the silver halide emulsion layer. 1c (σ); Depending on the layer structure, various layers may include a timing layer, an intermediate layer, a protective layer, and others, such as between a timing layer and a neutralization layer, containing an opacifying agent. The jlj combination is diagonally applied to It-rl of the silver halide emulsion layer and the silver halide emulsion layer.
C may also be provided with a layer of scavenger. When the 7tl itself is used as a scavenger, the mordant in the RP receiving layer may be the polymer according to the present invention or another void. When using the polymer related to non-exposure j as a scavenger, the amount added to the silver halide emulsion layer is the opposite to that of the image receiving layer as described above. 0.2.9 to 3 l/m' is recommended when adding to a layer located in II K, and when adding to a waste between a silver halide emulsion layer and an image-receiving layer. 20 m9 to 160 m7m” is fantastic. 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 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. 11 The dye used in the transfer dyeing method is Pontacyl green: / SN Ex (Pontacyl green
SN Ex; color index 737), Tartrazine (color index 640), acid magenta 0 (Ac1d Maze)
nta O; color index 692). Furthermore, the polymers according to the invention can also be used in optical filter layers, such as antihalation layers as described in U.S. Pat. No. 3,282,699. It contains a polymer, a filter dye mordanted by the polymer, and a hydrophilic binder. (Example) The present invention will be specifically explained below with reference to synthesis examples and examples, but the present invention is not limited by these. Synthesis Example 1 Synthesis of intermediate latex [poly-(divinylbenzene-costerene-N, N-dimethylaminomethacrylanilidene-N-vinylbenzylimidazole)] Stirring device, reflux tube, temperature side, 500 for nitrogen gas introduction and fitting
Pour 300 #Il of distilled water into a glass flask and stir under reflux for 30 minutes. Shume L
Flow the gas and (, is 1) up to 40'C? 1) Reject. Hevinylbenzene 11 Divinylbenzene 2.3p, l.
Lux H-45 (a condensate of alkylphenol with ethylene oxide), IJum salt,
Add 1 O, Oml (manufactured by Nippon Oil & Fats), 30
114'4' at a rotational speed of 0 rp+n). After that, it was heated at 65° (OW). When the monomer in Fujisco was uniformly emulsified,
-1 Distilled water 12ml VC Initiator obtained by dissolving potassium hydroxide A0.35.9 and anobiscyanovaleric acid 055I +7
gi'J't was added, and the warm melon was heated and stirred for 3116 minutes. After cooling to 1^, the desired product was obtained by passing through suction. lit latex solution 360 ml (solid content 11
．． Section 9) Synthesis ``Li 2 1!IL Show! 1 itself 6 synthesis J, -, jlL combination 6 Intermediate latex obtained in Example 1 360
ml, stirrer, reflux tube, thermometer, 1IXi To
- Pour the fi 00 ml in a 2-liter fusco and stir at room temperature for 30 minutes.
The mixture was stirred at a rotational speed of 0 Orpm. To this was added dropwise 110ml of acetonitrile over 1 hour, and then added 14.6ml of benzyl chloride. was added dropwise over 10 minutes. After heating this mixture and stirring for 30 minutes,
Heat to 5°C and hold for 6 hours. After cooling to room temperature, suction filtration was performed to obtain a latex liquid. After acetonitrile was distilled off under reduced pressure from this latex liquid, the latex was packed into a dialysis tube and dialyzed against deionized water. Concentrate the latex liquid after completion of Tosen and reduce the solid content to 5.
An example of 2-chi, YU liquid rate 59 cps (measured with B-type rotational viscosity index I) is 11. A latex liquid lJ3 of 6 was obtained. Synthesis Example 3 The same method as Synthesis Example 1 was used except that the following monomers were changed, and 365 ml of a latex solution of Polymer I was prepared (solid content: 1
2.9%). Hevinylbenzylimidazole 8.991 p-Meccroylaminobenzyrubenzyludimethino(-nnnn-'l:: = 25.0 g of rum chloride, styrene + 1.6.9. Divinylbenzene 2.3 p. wo,'ll1111111 1r11 Compound], 6.13.18 was synthesized according to the Synthesis Example.Meanwhile, as a comparative electrolyte, the following compound was synthesized according to JP-A No. 11jf!'i5-227 (I6 Specification 1). Comparison/Rification a) Thing (a) z
=4:48:48 Exemplary compound 1.6.13.18 and comparative polymer a,
b each 8114-hydroxymethyl-4-methyl-1
-Phenyl-3-pyrazoli 0.98.9° gelatin 8g 1 mucochloric acid 0.611.10% Emulgen-108 (polyoxyethylene nonylphenyl ether,
(manufactured by Kako Atlas Co., Ltd.) o, t5 mtVc water was added to dissolve the solution so that the finished amount was 250 d, and the coating amount was 2.5 mtVc.
The film was coated on a transparent polyethylene terephrate support with a thickness of 70 μm to form a first image-receiving layer. Table 1) of the above-mentioned image-receiving layer and comparative image-receiving layer, etc.
The layers are applied respectively to form an image receiving sheet 1. G, 13.1B. a and b. Second Noso gelatin (0,65,9β) and cryoxal (o
, o6,9/m) protective layer. Next, a photosensitive sheet 1 was prepared by sequentially applying the following 10 on a transparent polyethylene terephthalate sheet film support having a thickness of 180 μm. (1) The following magenta-purple image forming compound [1] (0,
8f//m ), diethyl laurylamide (0,49
/m ) and a layer containing gelatin (1,5,!9 sio). (2) Green-sensitive negative-working silver halide emulsion layer Green-sensitized negative-working silver halide emulsion (silver coating amount: 05 mq), potassium 2-octadecylhydroquinone-5-sulfonate (0
, 17,9β) and gelatin (1,3β). (3) J-containing gelatin (0.94 Vm'). The photosensitive sheet described above was exposed to light using wedges having different densities. It was then soaked for 20 seconds at temperatures of 23° C. and 32° C. in an activator solution having the following composition contained in a shallow tray type processor, and then passed between a pair of pressure rollers and superimposed on the image receiving sheet described above. Composition of activator solution Potassium hydroxide 56.2g 5-methylbenzotriazole 7.2g 11-aminoundecanoic acid 2.0g Potassium bromide 2.0.9 Finish to 100OCC with water. After a certain period of time, the photosensitive sheet and image-receiving sheet were peeled off, the image-receiving sheet was neutralized with acetic acid aqueous solution, and the reflection density (using a Sakura photoelectric densitometer PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.) was measured). Measurements were made over time using a green filter. The results are shown in Table 1. In the anterior capsule, for example, 18-1 shows a combination of the image-receiving sheet sample 18 and the photosensitive sheet 1. Same goes for the others. D2 and D5 in Table 1'VC above are 2 minutes and 5 minutes of processing.
D2/D represents the maximum transfer density in minutes, and D2/D is the ratio of the maximum density in 2 minutes and 5 minutes, and is a measure of the color image forming speed. A good mordant is one that exhibits strong mordant ability, has a rapid rate of color image formation, and does not cause migration such as desorption of dye. It can be seen that the polymers of the present invention all exhibit higher mordanting properties than the comparative polymers, have a good color image formation rate, and do not cause dye desorption. After treatment, a portion of each specimen was masked with black paper, the rest was exposed, and the specimen was placed in photobleaching conditions of 50,000 lux (measured at the surface), 35° C., and 53° relative humidity for 4 days. A light resistance test was conducted over the course of the test. Ratio of masking area density and non-masking area density of the same processing condition near θ D/DX100%=ρ Table I
I held up K. m D The above results show that the imidazole group-containing mordant has superior performance in terms of the photostability of dyes compared to the quaternary salt mordant, and the copolymer of the quaternary salt and imidazole of the present invention The combination has the excellent photostability of the imidazole group and the high mordanting properties of the quaternary salt. Example 2 In the same manner as in Example 1, image receiving sheets 1 and 6 having image receiving layers containing exemplified compounds 1 and 6, respectively, were prepared. On the other hand, as a comparative compound, the comparative polymer of Example 1 (aJ
and (bl) were used. Comparative polymers a and b were mixed so that the coating amounts of quaternary salt units and imidazole units were the same as those of exemplified compounds 1 and 6, respectively. Image-receiving sheets A and BQ were prepared having comparative image-receiving layers containing the following. Under the above conditions, the weight ratio of comparative compounds a and b was as follows. 2 Using the photosensitive sheet of Example 1, The results of measurements of dyeability and light resistance are shown in Table 2 after the same treatment as above.The symbols have the same meaning as in Example 1. It can be seen that the copolymer of the present invention has good dyeability and photostability of the dye, compared to ℃・ru, which has poor photostability.Example 3 Transparent polyester with a thickness of 180 μm (Ethylene terephthalate) The following layers were sequentially coated on a film support to prepare photosensitive sheet 2. (1) Neutralization layer poly(n-butyl acrylic tawny acrylic e) (weight ratio 30/70) 0) f9 ? Remar” 100 [1 Silane coupling agent as a hardening agent (manufactured by Toshi Silicone)
The coating amount of the polymer is 1 part in a methanol bath solution containing 2 parts.
Neutralizing layer coated by extrusion method so as to have 017/lri. (2) Timing layer made by hydrolyzing, lactonizing, and partially esterifying a vinyl acetate-maleic anhydride copolymer with an acid/butyl ester ratio of 15/85. 95 parts of the lactone polymer described in No. 54341 and poly(vinylidene chloride-methyl acrylate) (weight ratio 65/3015)
) with a polymer coating weight of 3.0 parts, i
A timing layer coated using an extrusion method using an acetone solution so that the ratio is i'/m'. (3) Cyan image-providing material having the following structural formula (064 g/r
rl), tricresyl phosphate C0,329/m
') and gelatin (L69/rtl). (4) Red-sensitive negative-working silver halide emulsion layer Red-sensitized negative-working silver halide emulsion (silver coating amount 0.3J7/g), 2
-sec-octadecylhydroquinone-5-potassium sulfonate (0,17, flm) and gelatin (0,
A red-sensitive negative-working silver halide emulsion layer consisting of 15 g/m 2 ). (5) Interlayer gelatin (0,63, lit/m') and 2-acetel-5-s'ec-octadecylhydroquinone (0,4
5 g/m', ). (6) Magenta coloring material layer Magenta image donor If'J (
0,8 g/m ), diethyl diurylamide (0,4,
? (7) Green-sensitive negative-working silver halide emulsion layer A green-sensitized negative-working silver halide emulsion (silver coating amount 0.5 g/lri). m)2-
Potassium octadecylhydroquinone-5-sulfonate (0,17 Ji'/m'') and gelatin (1,3 g/m'')
A green-sensitive silver halide emulsion layer consisting of rtl). (8) Interlayer gelatin (0.63 g/m ) and 2-acetyl-5-s
ec -octadecy/l/hydroquinone (0,45
(9) Yellow hue layer A yellow image-providing substance having the following structural formula (0,56,9/n
t ), tricresyl phosphate (0,2517 m
) and gelatin (olzg7rrt). (10) 7'i sensitive negative type silver halogenide emulsion layer 1'i
Color-sensitized negative silver halide emulsion (silver coating LL +1
．． 55 fl/m), potassium 2-octadecylhydroquinone-5-sulfonate (0,1711/m
) and gelatin (x3g/m')
Logenated fI (emulsion layer. (11) 111 layered gelatin (0.8ji/m), methacrylate beads (2~4711110.1597m) particle size 0.21
1 m of silica (0,45jj 7 m ) and tetrakis(vinylsulfonylmethyl)methane < 0.29/r
A protective layer consisting of rl). The photosensitive sheet described above was exposed stepwise using wedges having different densities. The image receiving sheet of Example 1 and the exposed photosensitive sheet were processed using the processing solution. After 5 minutes, the photosensitive sheet and image-receiving sheet were peeled off, and the reflection density (using a Sakura photoelectric densitometer PDA-60 manufactured by Konishiroku Photo Industry Co., Ltd.) was changed to red (λmax=64
4nm), green (λmax = 54 On+n), blue (
λmax = 434 nm) was measured using each filter, and the following results were obtained. In the table above, for example, 18-2 indicates a combination of image-receiving sheet sample 18 and photosensitive sheet sample 2. Same goes for the others. From 4' onwards, the four-pillar display is used. Furthermore, a light resistance test was conducted under the same conditions as in Example 1.
Tsuda. The resulting fading ratio ρD is shown in Table 4. Table 4 i'(43,4) shows that when using the photographic element of the present invention, the I)+nax is high, the mordant is high, the color image formation rate is fast, and the single color image formation rate is high. It has excellent storage stability, especially light resistance.Example 4 Among the multilayer photosensitive sheets 2 produced in Example 2, 211
11, 7. A multilayer photosensitive sheet 3 was prepared by replacing the 10 silver halide emulsion layers with the following silver halide emulsion. (4) Red-sensitive internal latent image type direct inversion bromide discount emulsion ( Silver coating amount 1.0 jil/m), 2-sec-octadecylhytroquinone-5-potassium sulfonate (o, l 7
jJl/rr: ), the nucleating agent shown in the above example (Kin 1
1.2 m9 per mole) and gelatin (1.5 g/m9)
) Red-sensitive silver halide emulsion layer (11E silver halide emulsion layer). (7) Green-sensitive internal latent image type silver bromide emulsion (silver coating amount 081/
yrl), potassium 2-octadecylhydroquinone-5-sulfosate (0,17&/rrj), the nucleating agent (1.2 µ/mol silver) and gelatin (+, 3.
! A green-sensitive silver halide emulsion layer consisting of 7/m'). (10) Blue-sensitive internal one-part latent image type silver bromide emulsion (Suzuki coated PiI
08g/m), 2-octadecylhydrocuginone-5-
A blue-sensitive silver halide emulsion layer consisting of potassium sulfonate (0.17 g/m,'), a pre-nucleating agent (1.2 mf/m) as described above) and gelatin (1.3 g/m'). The photosensitive sheet) 3 obtained above was exposed to prescribed light through a wedge with different densities in a stepped manner, overlaid with the image receiving sheet shown in the above example, and developed using the same alkaline processing solution as in the above example. I did it. 10 minutes later,
After peeling off the image-receiving sheet from the photosensitive sheet, the reflection densities (using a Sakura photoelectric densitometer PDA-60 model manufactured by Konishiroku Photo Industry Co., Ltd.) were measured for red (λmax = 644 nm) and green (λmax = 644 nm).
λmax = 54611m), blue (λmax = 4
34 nm), and the following results were obtained. The image-receiving sheet used in this study has excellent mordant properties and shows good images even when it is a photosensitive sheet using a direct positive emulsion. (Effects of the Invention) The objects of the present invention have been fully achieved and a new field of mordants suitable for photographic elements has been ushered in. Agent Sixmi Kuwabara

Claims (1)

[Scope of Claims] Having a layer containing a polymer represented by Iccho M+4 general formula (1) /[! A photographic element with a characteristic. General formula (1) [wherein A is at least two ethylenically unsaturated groups]
B is a copolymerizable monomer unit, B is a copolymerizable pJ-capable α
, a unit of a β-ethylenically unsaturated monomer. 117. is a hydrogen atom or a methyl group, ■(・2.R, and It is an al:) group, l(,5 and It6 are a hydrogen atom, an alkyl group or an aryl group. X is a monovalent anion. In addition, F, q, r and 3 represent copolymerized molti, and 60≧
P≧0 80≧q≧0 90≧r≧10 90≧I≧10. ]