JPS63247756A - Image receiving element for silver salt diffusion transfer process - Google Patents

Abstract

PURPOSE:To sufficiently improve the light shading and anti-curling properties of the titled element by providing with a layer contg. a cationic high polymer electrolyte together with an image receiving layer on the image receiving layer side of a supporting body, and specifying the coated amount of a hydrophilic colloid mounted on the rear surface of said body which is not provided with the image receiving layer. CONSTITUTION:The image receiving sheet is provided with at least the image receiving layer contg. a silver precipitant and the layer contg. the cationic high polymer electrolyte between the supporting body and the image receiving layer, on the supporting body. The light shading layer (1) contg. a black pigment and the hydrophilic colloid and a light reflecting layer (2) contg. a white pigment and the hydrophilic colloid are mounted on said rear surface of the supporting body, in this order. The light shading layer and/or the light reflecting layer contains a spherical particle having <=30 deg.C glass transition (Tg), and the coated amount of the hydrophilic colloid mounted on said rear surface of the supporting body is specified to 6-20g/m<2>. Thus, the anti- curling effect of the titled element is prevented, and said effect is remarkably displaced in the case that the hydrophilic colloid mounted on said rear surface of the supporting body does not contains a polyol compd. contg. >=2 hydroxy groups.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver salt diffusion transfer method. More specifically, the present invention relates to a so-called peel-off type (beer-apart type) image receiving element for use in a silver salt diffusion transfer method.

(Prior Art) Diffusion transfer photography using silver salts such as silver halides has been known. In such a photographic method, a light-sensitive element containing an exposed silver halide photographic emulsion and a receiver (JR element) containing silver deposition nuclei are superimposed, and these λ
It is well known to obtain a positive silver image directly on an image-receiving element by applying an alkaline processing solution containing a silver halide solvent between the two elements in the presence of a developing system. .

In this method, an unexposed silver halide emulsion in a light-sensitive element is dissolved in a silver halide solvent and released as a silver ion complex into an alkaline processing solution, transferred to an image-receiving element, and transferred to an image-receiving precious element. A positive image is directly formed by precipitation as a silver image by the action of silver precipitation nuclei.

However, the silver image formed on the image-receiving element thus obtained has the disadvantage that it is easily discolored or faded during storage.

As a method to improve this drawback,
, American painting patent! ,! 33,712 and British Patent l, 76
≠ and 6442 each describe a method of applying a water-soluble polymer solution f containing an alkali neutralizing component gold to the surface of the obtained silver image.

However, with this method, it takes a considerable amount of time for the narrow surface coated on the polymer water bath to completely dry, and during that time, the surface is sticky and sticky, making it impossible to overlay the print layer, and fingerprints. Often, dirt and dust were attached. Further, it is troublesome to further apply such a liquid to a silver image.

The specification of Japanese Patent Publication No. 1 T-titi 4 Cir states that (1) cellulose, which is hydrolyzable and which becomes alkali-permeable upon hydrolysis, contains a compound that is diffusible and can change the properties of the silver image; Disclosed are elements comprising an ester, polyvinyl ester or polyvinyl acetal layer and thereon (II) a recycled cellulose layer containing silver deposition nuclei.

Organic mercapto compounds have been described as compounds that can be diffused and can change the properties of silver images.

゛・Or Special Publication Showa 36-2/, lμO% Special Publication Showa-
ZOO, Hiroshi 31 discloses that fading of a silver image is prevented by allowing a metal oxide to act on the silver image.

However, these organic mercapto compounds and precious metal compounds must be incorporated in large amounts in order to preserve the silver image, and they may cause stays or have undesirable effects on the image forming speed. It was found that this was accompanied by problems such as:

In our earlier invention (% Application No. 60-23≠≠), as a new image stabilizing means, we provide a silver salt diffusion transferable photographic element using a silver halide emulsion layer containing at least silver iodide as a photosensitive layer. , a silver salt diffusion transfer method characterized in that the image receiving element has an image receiving layer containing at least chiral deposition nuclei on a support, and the image receiving element has an iodide ion trapping layer between the image receiving layer and the support. The picture element is shown.

Furthermore, in Japanese Patent Application No. AO-23116, an image-receiving layer containing at least silver deposition nuclei is provided on a support, and an acetic acid film having a degree of acetylation between 30 and 300 is provided between the support and the image-receiving layer. A silver salt diffusion transfer photographic element is also shown which is characterized by having a layer comprising cellulose and a cationic polyelectrolyte.

On the other hand, as a result of development, a transferable silver complex salt is formed and diffused in the form of an image of transferred silver 1 into the image-receiving layer on another support.
Habits are formed. The image-receiving sheet is peeled off from the photosensitive sheet in order to obtain the desired positive print or slide, but the peeled image-receiving sheet is free of shadows from its constituent layers such as the neutralizing layer and image-receiving layer, as well as coating history. It has become clear that this causes curling during storage after peeling, and that it becomes even worse when the cationic polymer electrolyte layer is applied.

(Problems to be Solved by the Invention) In order to improve the above-mentioned drawbacks, at least 11) a light-shielding material containing a black pigment and a hydrophilic colloid is added to the back side of the image-receiving sheet (the side that does not have an image-receiving layer). (2) The image-receiving element having a light-reflecting layer containing a white pigment and a hydrophilic colloid has improved light-shielding properties, anti-curl properties, and writing properties.Furthermore, simultaneous multilayer coating of a light-shielding layer and a light-reflecting layer is possible. It becomes possible.

When the peeled image-receiving sheet deteriorates in curl over time, the curl after peeling can be improved by increasing the amount of hydrophilic colloid applied.

However, with the layer structures (1) and (2) above, immediately after the image-receiving sheet is peeled off from the photosensitive sheet, the image-receiving layer tends to curl as it absorbs moisture in the processing solution. Ninth, in order to quickly remove such curls, it has been discovered that applying heat with a hair dryer to rapidly reduce the moisture in the processing solution has the drawback of causing cracks in the back layer. . Furthermore, it has been found that when diffusion transfer processing is performed under low humidity, the back layer is cracked during processing due to the rubbing with a processing roller, resulting in light leakage.

(Object of the invention) An object of the invention is to provide an image receiving element for silver salt diffusion transfer method, which contains a back layer having sufficient light blocking properties, anti-curl properties, and also has writable gold. .

Another object of the present invention is to provide an image-receiving element for silver salt diffusion transfer method which has a good image preservation property.

Another object of the present invention is to provide an image-receiving element for silver salt diffusion transfer, which has a back layer with good heat resistance.

Another object of the present invention is to provide an image-receiving element for silver salt diffusion transfer that has a light blocking ability even under low humidity.

It is a further object of the present invention to provide a photographic film unit for peelable diffusion transfer including such an image receiving element.

(Means for Solving All Problems) As a result of intensive research, the present inventors have found that an image receiving layer containing at least a silver precipitant is provided on a support, and a cationic polymer is provided between the support and the image receiving layer. #! In an image receiving element for salt diffusion transfer method having a layer containing an electrolyte, a light shielding layer containing a black pigment and a hydrophilic colloid (11), (2 ) A light-reflecting layer containing a white pigment, a hydrophilic colloid, and gold, the light-shielding layer and/or the light-reflecting layer having a glass transition point (Tg) of 300.
We have discovered that this is possible with an image-receiving element for silver salt diffusion transfer method, which contains gold spherical particles having a particle size of C or less and has a hydrophilic colloid coating amount of 6 to 20 t/m2 on the puncture side Ta.

The hydrophilic colloid used in the present invention is preferably gelatin, phthalated gelatin, polyvinyl alcohol,
Polyethylene oxide, polyacrylamide, polyvinylpyrrolidone, polyethyleneimine, polyacrylic acid, hydroxyethyl cellulose, carboxymethyl cellulose (D cellulose derivative). Particularly preferred is gelatin.

The total coating amount of hydrophilic colloid varies depending on the coating material and amount on the image-receiving layer side and the coating amount of the skin containing cationic polymer electrolyte fX, but is 6 to 20 t/m2, preferably I-/j.
ri/m2.

From the viewpoint of the effects of the present invention, it is preferable that the light-shielding layer and/or the light-reflecting layer do not contain mboriol containing λ or more hydroxyl groups.

The black pigment used in the present invention is preferably carbon black. As a raw material for carbon black, carbon black produced by any method such as channel thermal or furnace can be used; the particle size of carbon black is not particularly limited, but carbon black having a particle size of 0 to 100 mm is preferable. Also, Tokukai Aki? - Grafted carbon black as described in P7/≠λ can also be used.

The amount of black pigment added as a light-shielding agent can be adjusted according to the sensitivity of the photosensitive material to be light-shielded, but the optical density! ~/θ is preferable.

In the light-shielding layer of the present invention, the black pigment/hydrophilic colloid weight ratio is preferably /, j to 0./, more preferably from the viewpoint of light-shielding ability and film brittleness (causing cracks). / is 0 to 2.0.

Further, as the white pigment, titanium oxide, barium sulfate, and zinc oxide are preferable. Particularly preferred is μ titanium oxide, and titanium oxide surface-treated with silica and/or alumina zinc oxide, a silane coupling agent, etc. is particularly preferred.

The amount of white pigment added as a light reflecting agent may be adjusted appropriately depending on, for example, how much writability is required.
, 0=Ij? /m2 is used B,j ~/017m2
is preferred.

In the light reflecting layer of the present invention, the white pigment/hydrophilic colloid weight ratio is preferably 3 to /j1 from the viewpoint of layer density N (cohesive failure occurs within the layer), and particularly preferably It is 1-10.

(9) If a material with high hardness, such as titanium oxide, is on the outermost layer, when friction occurs with a material with low hardness, it may be scraped off and adhere to the surface, staining the film. The upper layer of the light-reflecting layer further contains hydrophilic colloid! It is preferable to use i#. This retention layer can be coated in three layers at the same time, including a light-shielding layer and a light-reflecting layer made of hydrophilic colloid.

The spherical particles used in the present invention have a Tg of J00C or less, more preferably an sTg of 10°C or less.

Examples of the spherical particles used include polyisoprene,
Polyethylene, polypropylene, polyethyl acrylate, polybutyl acrylate 1 poly-5ec-butyl acrylate, polypropyl acrylate, polyhexyl acrylate, polymethoxybutyl acrylate, poly N-octylacrylamide, polybutyl methacrylate, polycoethylhexyl methacrylate, Polyoctadecyl methacrylate, poly(vinyritene chloride-co-acrylonitrile-co-acrylic acid) (4,t:/conijmole%), polyvinyl acetate, poly(styrene-co-butadiene-co-acrylic acid) (uO: II:
2 mole%), poly(methyl methacrylate-co-ethyl acrylate) (sosyomo1e%'), poly(ethyl methacrylate-co-ethyl acrylate))
(JO: j47 mole), poly(butyl acrylate toco 2-acrylamido-2-methylpropanesulfone [)' (rit: co mole%), poly(ethyl acrylate toco acrylic acid) (ri7: J mole%)
, poly(butyl methacrylate-coptyl acrylate-comaleic acid) ($O:jP:/mole),
polymethacrylate-co-butyl acrylate-co-ethyl acrylate) (30:zO:20mole
To), and other Re5search Dis
It is also possible to use the latex described in Closure July 10, 1999, which has a Tg of 3 o 0 c or less.

Particularly preferred are polyethyl acrylate, polybutyl acrylate, and polypropyl acrylate.

The diameter of the spherical particles is preferably 0.0Q/~lμ. More preferably O6.

OO! 〜O0jμelectricity. Even more preferably, o
, oi-o, ittm.

From the viewpoint of cracking and less fabricability, the spherical particles/hydrophilic binder (weight ratio) in the layer containing spherical particles is preferably i, o to 0. It is O/.

More preferably, it is O0j to 0.7.

These spherical particles work very effectively together with hydrophilic colloids in preventing cracks and curling of damaged sheets. The preferred amount of spherical particles with a Tg of 30°C or less is 0. j~, tf/z 2.

The spherical particles can be produced by a method well known to those skilled in the art, such as a conventional emulsification process or emulsification of a synthetic resin. When preparing these, reference may be made to the plastic emulsion edited by Taira Okuda and Hiroshi Inagaki (Kobunshi Kankankai).

Furthermore, in order to impart adhesion resistance to the back layer of the present invention, it is preferable to add a matting agent'tm to the above-mentioned protective layer.

Preferred examples of the matting agent include organic compounds such as water-dispersible vinyl polymers such as polymethyl methacrylate, cellulose acetate propionate, and starch. As the inorganic compound, silver halide, stro/barium sulfate, calcium carbonate, silicon dioxide, magnesium oxide, titanium oxide, etc. are preferably used.

As a matting agent, a polymer having a gala δ transition point (Tg) of 30°C or more is preferable, and a polymer having a Tg of jO'c or more is more preferable. Polymethyl methacrylate, polyethyl methacrylate, poly 5ec-butyl methacrylate,
Poly tert-e-rt-butyl methacrylate, polyadamantyl methacrylate, poly 1s6-propyl methacrylate, poly tert-butyl acrylate, polyacrylonitrile, polyacrylonitrile, polyvinyl benzoate, polystyrene, polypromustyrene, polyterchlorstyrene, poly Termethoxystyrene, poly-(methyl methacrylate-coptyl methacrylate) (rj:/jmole ratio), poly(sterene-coethyl methacrylate) (fOSJOmole ratio)
, poly(methyl methacrylate i:!-butyl acrylate tocoacrylic acid) (to:it:, 2mole9
b), poly(ethyl methacrylate-cobuter methacrylate-co-maleic acid) (7!: 23:
2mole%), poly(methyl methacrylate-codester methacrylate-co-coacrylamide-comethylpropane sulfone [(fO:/7:jmole%
), poly(sterene-co-butyl methacrylate-co-2-hydroxyethyl methacrylate) (70:λj
:jmole%), poly(methyl methacrylate-co-ptylacrylate-co-acrylamide) (77:,
z/:2m01e*), poly(ethyl methacrylate-coptyl methacrylate-co-methacryloyloxypropanesulfonic acid) (70:Jf:JmotsJ), and the like.

Particularly preferred is polymethyl methacrylate.

If the size of the matting agent particles is too large, problems will occur, such as sinking of the particles into the light-shielding layer and light-shielding leakage (pinholes) due to multilayer coating at 11ff1. Preferably, the particle size of the matting agent particles (as the diameter of spherical particles) is 75μ.
The average particle size is 73m% and 10μm. More preferably, the average particle size is /1i'm"jt μm. Even more preferably, the average particle size is 2 to ≠ μm.

The particle size distribution of the matting agent particles used in the present invention is as follows:
It can be wide or narrow. However, as mentioned above,
In order not to cause insufficient light-shielding ability (optical pinhole), particles larger than particle size/jμm should not be included; on the other hand, particles with a particle size o that are virtually ineffective in improving adhesion resistance
, iμm or less. That is,
A preferred particle size distribution is 001 μm 1-it μm.

More preferably 0. Jr-10 μm. More preferably, the range is /μm to ioμm.

In the retention layer of the present invention, the weight ratio of matting agent particles/hydrophilic colloid is preferably 3 to 0.7. More preferably /, t-0,2.

(9) The back layer used in the present invention is preferably water resistant, and for that purpose it is preferable to add a hardening agent (it does not matter which back layer it is added to). As the hardening agent, those well known to those skilled in the art can be used, and the amount thereof is preferably 0.3 to 7% by weight based on the total hydrophilic colloid.

The support used in the present invention may be transparent or opaque, but
Preferably, the material does not undergo significant dimensional changes during processing. Examples of such supports include cellulose acetate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, baryta paper, and water-impermeable paper such as polyethylene, which are used in common photographic materials. Examples include paper laminated with polymers.

To obtain a white background, a whitening agent such as titanium oxide or barium sulfate may be added to the support, or the above-mentioned whitening agent may be coated on the support.

A preferred embodiment of the image-receiving layer constituting the image-receiving sheet of the present invention is a substance (referred to as a silver precipitant substance or development nucleus) that catalyzes the reduction reaction of a water-soluble silver complex in the silver salt diffusion transfer method.
A layer containing an alkaline treatment composition in a permeable binder.

Silver precipitating substances include zinc, mercury, lead, cadmium,
Heavy metals such as iron, chromium, nickel, tin, cobalt, and copper; precious metals such as palladium, platinum, silver, and gold; and sulfides, selenides, and tellurides of these heavy metals.
All conventionally known silver precipitants can be used. These silver precipitant materials can be used either by reducing the corresponding metal ion to create a metal colloidal dispersion or by mixing a metal ion solution with a soluble sulfide, selenide or telluride bath solution. Therefore, water-insoluble metal sulfides and metal selenides can be obtained by making colloidal dispersions of metal tellurides.

To obtain an image-receiving element that gives a favorable tone image, these silver precipitant materials are typically present in the image-receiving layer at lo 10
~1O-5t/α2, preferably 10-8~10'
Include t/mer 2.

The above-mentioned binders include hydrophilic binders such as gelatin, polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, etc., but particularly suitable are binders made of alkali-impermeable polymers made alkali-permeable by decomposition.

Examples of decomposable alkali-impermeable polymers include cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose propionate, and cellulose acetate butyrate, as well as polyvinyl acetate, polyvinyl propionate, and polyvinyl chloroacetate. There are polyvinyl esters such as. This
An alkali-impermeable polymer layer made of at least one of these polymers becomes alkali-permeable by decomposition with an alkaline solution. In addition, polyvinyl acetals such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral can also be used. In this case, it can be made permeable to alkali by acidic hydrolysis.

To make a single layer of an alkali-impermeable polymer permeable to alkali by alkali decomposition, an alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or tetraalkylanthenium hydroxide is mixed with methanol or ethanol fk (
A saponification solution is prepared by dissolving alcohol (water bath solution) containing D alcohol at a concentration of tlo~100, and this saponification solution is brought into contact with a layer of an alkali-impermeable polymer such as cellulose ester. As for the contacting method, any conventionally known contact means such as brush application, roller application, air knife application, spray application, or immersion in a saponification solution bath can be used. At least the surface of the alkali-impermeable polymer layer is saponified by contact with the saponifying solution. It is also effective to add t-/-20 weight percent of a polyhydric alcohol or fc derivative containing two or more hydroxyl groups to the alkaline saponification solution.

The saponified n-th layer becomes permeable to alkali and can be penetrated by a diffusion transfer processing solution.

To prepare an image-receiving layer for the silver salt diffusion transfer method, cellulose ester, such as cellulose diacetate, is impregnated with a silver precipitant by vapor deposition, coated on a support with a hole diameter, and decomposed with an alkali. A method in which a silver precipitant is prepared on the spot by reacting silver nitrate and sodium sulfide in a solution, and the silver precipitant is applied onto a skinned body and then decomposed with alkali. m
A method of embedding a silver precipitant in the n-layer that is decomposed during alkali decomposition, and a method of embedding a silver precipitant in the n-layer that is decomposed at the same time when the cellulose ester layer is decomposed with an alkali to produce regenerated cellulose, and then silver chloride is added in the decomposed n-th layer. A method of creating a silver precipitant by reacting an acid with a reducing agent can be used.

It is preferable to use a film-forming acidic polymer for the neutralizing layer that can be used in the image-receiving sheet of the present invention, and any such acidic polymer can be used. Examples of acidic polymers include copolymers of maleic anhydride, such as styrene-maleic anhydride copolymers, methyl vinyl ether-maleic anhydride copolymers, ethylene-maleic anhydride copolymers, and copolymers of maleic anhydride and ethylene. Monobutyl ester of a polymer, monobutyl ester of a copolymer of maleic anhydride and methyl vinyl ether, monoether ester of a copolymer of maleic anhydride and ethylene, monopropyl ester of the same copolymer, Monopentyl ester, monobenzyl ester of the same copolymer, monoether ester of the copolymer of maleic anhydride and methyl vinyl ether, monopropyl ester of the same copolymer, monobenzyl ester of the same copolymer, monobenzyl ester of the same copolymer Monohexyl esters, etc. of: polyacrylic acid; polymethacrylic acid; copolymers of diacrylic acid and methacrylic acid in the same ratio; diacrylic acid or methacrylic acid and other vinyl-based heptamers, such as acrylic esters (e.g. acrylic acid butyl, etc.), methacrylic acid esters, vinyl ethers, acrylamides, methacrylamides, etc., preferably acrylic acid or methacrylic acid content.
A copolymer of Q to O molti and the like can be used.

Among these acidic polymers, it is preferable to use polyacrylic acid, acrylic acid-butyl acrylate copolymer, or maleic anhydride-methyl vinyl ether copolymer. The above-mentioned Chinese centrum polymers may be used alone or in combination of two or more. Further, for the purpose of increasing the film strength, etc., a cellulose conductor such as acetyl cellulose, a T-conductor, or other polymer may be mixed with the above-mentioned acidic polymer.

For example, gelatin, polyvinyl alcohol, polyacrylamide, partially hydrolyzed polyvinyl acetate, a copolymer of β-hydroxyethyl methacrylate and ethyl acrylate, or acetyl cellulose is used as the main component for the neutralization timing 1fI. Samana, and other US patents 3. ≠j.

tlr No. 6, J, ll-2/, No. 193, No. 3, 71
! , I/! Same issue! , r Hiro 7. BLJ issue, Mukaihiro.

00ri, No. 030, JP-A-Shojλ-/Hiroshi, μ/! You can also use those listed in the No. Furthermore, the above-mentioned neutralization timing layer and, for example, the US patent≠, O! 6,3ri≠No., Dohiro, 061. ≠ri No. 6, JP-A-63-7.2.1.22
It is also possible to use a single layer of a polymer whose permeation of an alkaline processing liquid has a large temperature dependence, as described in No. 1 or Japanese Patent Application Laid-open No. 2003-120000-7F, No. 30.

In addition, the neutralization timing layer may also contain a highly efficient polymerization product that can undergo β-dissociation in an alkaline environment.

The undegraded portions of the cellulose ester layer containing acetylcellulose as an aspect of the receiver for silver salt diffusion transfer are suitable for improving the tone, stability, or other photographic properties of the silver transfer image. IB or son
The above-mentioned mercapto compounds may be included. Such mercaptated molecules are utilized during imbibition by diffusing from the 'rLfc position where they are initially placed. This type of receptor element was created by Richard Doublenie Young (Riccha).
rdW.

Young) in U.S. Pat.

In addition, between the layer of decomposed n* cellulose ester containing a silver precipitant as necessary and the lower layer of cellulose ester or partially decomposed cellulose ester (which may contain the above-mentioned mercapto compound). Another hydrophilic polymer N4 may be provided. Examples of polymers used in this hydrophilic polymer layer include gelatin, V1 conductor gelatin (such as phthalated gelatin), sugars (such as starch, galactomannan, gum arabic, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, and pullulan). , hydroxypropylcellulose, etc.), hydrophilic polymers (e.g., polyacrylamide, polymethylacrylamide, poly-N-
vinylpyrrolidone, λ-hydroxyethyl methacrylate, etc.).

The cationic polymer electrolyte used in the cationic polymer electrolyte-containing layer of the present invention is preferably a cationic polymer electrolyte that does not contain iodide ions, and various known quaternary ammonium salt (or phosphonium salt) polymers can be used. The quaternary ammonium salt (or phosphonium salt) polymer is
It is widely known as a mordant polymer or an antistatic polymer from the following publications.

JP-A-166-01 U.S. Patent 3. ri sr, ri5Pt, JP-A Show jtj-/≠233 ri, JP-A Show! Hiroshi/
21. , 0λ7, JP-A-11-ZR.

r3! , JP-A-33-30321% JP-A-KAI! ≠−ta 22
Water-dispersed latex described in US Pat. No. 7≠; US Patent 2.
j4#, jtlA, P, 3. /4#, 04/, same j,
714, polyvinylpyridinium salts described in r/pi;
Water-soluble quaternary ammonium salt polymers as described in U.S. Pat.

A preferred cationic polymer electrolyte is represented by the following general formula.

In the formula, the proportion of ethylenically unsaturated monomer is expressed. R1
represents a hydrogen atom, 'fi- represents a lower alkyl group k having from 1 to about 6 carbon atoms, and L represents a divalent group having from 1 to about 72 carbon atoms. R25R3 and R4 are each the same or different alkyl groups having 1 to about -0 carbon atoms, or aralkyl groups having 7 to about 0 carbon atoms; %R2, R3 and R4 are each They may be connected to form a cyclic structure together with Q. Q is N or P, and Ma9 represents an anion other than iodide ion. X is O to about O7, and y is about 10 to 700 molar.

Examples of ethylenically unsaturated monomers A include olefins (e.g. ethylene, propylene, l-
butene, vinyl chloride, vinylidene chloride, isobutyne, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chloroprene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, allyl acetate, vinyl propane, etc.); pionate, vinyl butyrate, vinyl benzoate), esters of ethylenically unsaturated acids (such as methyl methacrylate, butyl methacrylate, tart-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, octyl methacrylate) , amyl acrylate, coethylhexyl acrylate, benzyl acrylate, maleic acid dibutyl ester, fumaric acid diethyl ester, ethyl crotonate, methylene malonic acid dibutyl ester), styrenes (nine, styrene, α-methylstyrene, vinyl toluene,
chloromethylstyrene, chlorstyrene, dichlorostyrene, bromstyrene, etc.), unsaturated nitriles (such as acrylonitrile, methacrylaterile, allyl cyanide, crotonitrile, etc.). Among these,
Styrenes and methacrylic acid esters are particularly preferred from the viewpoint of emulsion polymerizability, hydrophobicity, etc. A may contain at least one of the above monomers.

From the viewpoint of polymerization reactivity, the hydrogen atom or methyl group in R1 is preferably used.

-C-N-R5-1 In the above formula, R5 represents alkylene (e.g., methylene, ethylene, trimethylene, tetramethylene, etc.), arylene, aralkylene (e.g., alkylene having an evaporator) from the viewpoint of alkali resistance. ) and sR6 represents a hydrogen atom or R2 group. n is an integer of 1 or λ.

Q is preferably N in view of the toxicity of the raw material.

Xe is an anion other than iodide ion, such as halogen ion (for example, chlorine ion, bromide ion, etc.), alkyl sulfate ion (for example, methyl sulfate ion, ethyl sulfate ion, etc.), alkyl or aryl sulfonate ion (for example, Examples include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonate), 61 [ion, acetate ion, and sulfate ion. Among these, chloride ions, alkyl sulfate ions, arylsulfonate ions, and nitrate ions are particularly preferred.

The alkyl and aralkyl groups of R2% Ra and R4 include substituted alkyl groups and t% aralkyl groups.

Examples of the alkyl group include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, st-phther group, hexyl group, cyclohexyl group, coetherhexyl group, and dodecyl group, and f-substituted alkyl groups such as alkoxyalkyl group. (e.g., methoxymethyl group, methoxybutyl group, ethoxyethyl group, butoxyethyl group, vinyloxyethyl group, etc.), cyanoalkyl group (e.g., cocyanoethyl group, 3-cyanopropyl group, etc.)
, halogenated alkyl groups (e.g., 2-fluoroethyl group, 2-chloroethyl group, no-fluoroflopyl group), alkoxycarbonylalkyl groups (e.g., ethoxycarbonylmethyl group, etc.), allyl group, copenyl group, propargyl group, etc. There is.

Aralkyl groups include unsubstituted aralkyl groups, such as benzyl, phenethyl, diphenylmethyl, and naphthylmethyl groups; substituted aralkyl groups, such as alkylaralkyl groups (e.g., ≠-methylbenzyl,
2. j-dimethylbenzyl group, Hiro-isopropylbenzyl group, ≠-octylbenzyl group, etc.), alkoxyaralkyl groups (for example, Hiro-methoxybenzyl group, ≠-antafluoroprobenyloxybenzyl group, μ-ethoxybenzyl group) ), cyanoaralkyl groups (such as Hiro-
cyanobenzyl group, co(≠-cyanophenyl)benzyl group), halogenated aralkyl group (f:, e.g. 11 μm chlorobenzyl group, 3-chlorobenzyl group, μ
m-bromobenzyl group, m(≠-chlorophenyl)benzyl group, etc.

The alkyl group preferably has 7 to 72 carbon atoms, and the aralkyl group preferably has 7 to 72 carbon atoms.

Examples of R2% R3 and R4 interconnecting to form a complete cyclic structure with Q include the following.

An example of an aliphatic heterocycle (representing an atomic group necessary to form a J ring) is, for example, R4. n is an integer from λ to /ko].

It represents a hydrogen atom, the number of carbon atoms, and a lower alkyl group. ), represents an atomic group required to form a Zen ring), and R
Represents 2. R2 may be the same or different in the two cases. ) etc.

Among these ring structures, R2, R4, R6, Q and X○ in the above examples have the same meanings as in general formula (1).

Of course, the y component may be a mixture of two or more components.

X is preferably 20 to 60 moles and y is preferably ≠Q to rO moles.

In addition, a monomer having at least two ethylenically unsaturated groups (preferably 2 to μ) is copolymerized so that it does not migrate from one desired layer to another in the image-receiving element and have undesirable photographic effects. It is particularly preferable to use it as a cross-linked aqueous polymer latex.

Examples of copolymerizable monomers having at least λ ethylenically unsaturated groups are, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, neo-interglycol dimethacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, etc. Methacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, tetramethylene glycol diacrylate, trimethylol bromine triacrylate, allyl methano 1 slate, allyl acrylate, diallyl phthalate, methylene bis acrylamide, methylene bis methacrylamide, trivinylcyclohexane,
Divinylbenzene, N,N-bis(vinylbenzyl)-
N,N-dimethylammonium chloride, N,N-diethyl diN-(meth9.tacryloxyethyl)-N-
(vinylbenzyl)ammonium chloride, N.

N,N',N'-tetraether-N,N'-bis(vinylbenzyl)-p-xylylenediammonium dichloride, N,N'-bis(vinylbenzyl)-triethylenediammonium dichloride, N,N,N '
, N'-tetrabutyl-N, N'-bis(vinylbenzyl)-ethylenediammonium dichloride, and the like. Among these, divinylbenzene and trivinylcyclohexane are particularly preferred from the viewpoint of hydrophobicity, alkali resistance, and the like.

Next, I will give examples of compounds.

Compound example ■ X: Y: Z"10: Hiroj: Hiru j ■ x: y=j: ri! H3 These iodine ion scavengers are used to determine the specific position of the image-receiving graft,
Preferably, when the alkali neutralizing layer and the neutralizing timing layer are combined between the image receiving layer and the support, the alkali neutralizing layer and the neutralizing timing layer are combined, or between the alkali neutralizing layer and the neutralizing timing layer, or between the support and the alkali neutralizing layer. It is best to set it in between. The coating amount of the cationic polymer electrolyte is 0°3 to 70g/m2, preferably o,
z~p,.

g/m2 is good.

These cationic polymer electrolytes are mixed with an appropriate binder (cellulose acetate, polyvinyl alcohol, gelatin, polyacrylamide, etc.) as necessary, and various known additives (hardening agent) are added as necessary. , coating aids, brighteners, pigments, etc.) and apply by known means.
Dry.

A particularly preferred binder is cellulose acetate.

The mixing ratio of cellulose acetate to the cationic electrolyte is: cellulose acetate f:0, j~μ.

A range of 0 times is preferred.

Although the image-receiving sheet of the present invention may further include a photosensitive layer on the same support, it is preferable that the image-receiving sheet does not include a photosensitive layer. That is, the photosensitive layer is coated on a support separate from the image-receiving sheet: A
The second photosensitive sheet structure 5y is preferably a component of a photographic film unit, in which the image receiving sheet and the photosensitive sheet are provided with a processing liquid container which can be ruptured under pressure and contains a processing liquid between the two sheets. Preferably, it is in the form of

The image-receiving element may contain various treatments, such as a hardening agent, a fluorescent whitening agent, and a coating aid, as required.

As the photosensitive element, those conventionally known in the field of silver salt diffusion transfer method are used. The silver halide photographic emulsion contained in the sensitive material element is silver halide grains having a silver halide composition of preferably 1 silver bromide and 1 silver iodobromide, and an average grain size of 3 μ or less; A latent image is mainly formed on the particle surface.
This is a silver halide photographic emulsion containing silver halide grains. Further, as a binder, a hydrophilic colloid such as gelatin is usually used.

The silver halide photographic emulsion described above is preferably μ chemically sensitized,
Furthermore, it is spectrally sensitized by methine dyes. Furthermore, chemical compounds such as azoles are added to photographic emulsions such as those described above for the purpose of preventing formation of continuous layers or stabilizing photographic performance.

The photosensitive element preferably has a hydrophilic colloid layer (for example, a protective layer) other than the photographic emulsion layer on the support, and the photographic emulsion layer or other hydrophilic colloid layer contains a coating aid, an antistatic agent, A capping agent, a plasticizer, a development accelerator, a hardening agent, a filter dye, an ultraviolet inhibitor, etc. can be added.

Examples of developing agents used in the present invention include hydroxyamine developers such as N,N-diethyl-hydroxylamine, N,
Diethylhydroxylamine and N in N-bismethane
, N-bis-ethoxyethyl-hydroxylamine is preferably used.

A phenidone compound may be used in combination as an auxiliary developer.

The processing composition used in the present invention preferably contains a silver halide solvent such as U.S. Pat.
rj7,27! Contains all of the cyclic imides (for example, uracil, urazol, !-methyluracil) described in No., No. 137° Core No. 6.

The treatment composition typically contains alkalis (e.g. alkali metal hydroxides, e.g. sodium hydroxide, potassium hydroxide),
Contains all heavy film-forming agents (e.g. hydroxyethyl cellulose, sodium carboxymethyl cellulose) and further contains other compounds known in the silver salt diffusion transfer process,
For example, antifoggants, color toning agents such as mercapto compounds,
Stabilizers such as oxyethylamino compounds may be included.

(Example) The present invention will be explained in further detail below by giving Examples and Comparative Examples.

Example/Preparation of image-receiving sheet Preparation of image-receiving sheet (1) The following layers were sequentially formed on a polyethylene laminate paper support to prepare an image-receiving sheet ti+1-. Values within 0 are expressed in coating amount kf/m 2 .

1) Neutralization layer: Cellulose acetate (degree of acetylation j3) (6), methyl vinyl ether-maleic anhydride copolymer 0 (μ), Uvitex OB (trade name of Ciba Geigy)
(0,0μ) 2) Cationic polymer electrolyte layer Cellulose acetate (acetylation [←I) (≠, λ), the following compounds (K, RI 3) Neutralization timing layer Cellulose acetate (degree of acetylation! Ma-) ( r, j), /-(4
! -hexylcarba7ylphenyl)-co,J-dihydroimidazole-2-thione <o, ot) 4) Image-receiving layer cellulose acetate (degree of acetylation jJ) (/, -1), radium sulfide (7, zxio), 1-(IA-hexylcarbamoylphenyl)-λ.

3-dihydroimidazole-2-thione (0°02)f
After coating, add sodium hydroxide and θt to 3 methanol.
Dissolve 001F16 and saponify the surface using saponification solution to form an image-receiving layer.

5) Peeling layer Butyl methacrylate-acrylic acid copolymer (molar ratio/!: r (0, OJ) The following Table 1 was applied to the back side of the support containing the entire image-receiving layer thus prepared. An image-receiving sheet /-/-/-2 was prepared by applying a back layer as shown in 90. However, the symbols in the table are: CB: Carbon black Gel: Gelatin any: Glycerin PEA: Polyethyl acrylate spherical particles (average diameter o , or μm) Ti02: Titanium white PMMA: Polymethyl methacrylate Matting agent (average particle size: !μm).

Preparation of Photosensitive Sheet The following layers were sequentially provided on the support (black polyester film): 1) Silver iodobromide (iodine content 6°! morch) with an average grain size of 1.0 μm (silver content o, r rit/rrL2), gelatin (J
, J) 2) Protective layer Gelatin (o,'y)s Polymethyl methacrylate particles (0,/) Preparation of processing solution (1) Curl evaluation Layer the unexposed photosensitive layer sheet and the above image-receiving layer sheet and place between them. The above processing solution was spread at a float of 0.011 tyi, and diffusion transfer development was performed. After 30 seconds, both sheets were peeled off in an atmosphere of 2t"C to obtain a processed image receiving sheet.

This processed image-receiving sheet is
Cut it into pieces of size rrL and leave it under the conditions of 210C, relative humidity 201R, 1 month and 1ROQB for a long time.Place the above image-receiving sheet on a flat surface and measure the height from the flat surface to the edge of the image-receiving sheet. The curl value was measured. Positive curl is when the image-receiving layer has a concave surface, and negative curl is when the image-receiving layer has a convex surface.

(2) Diffusion transfer cracking n optical fog evaluation under low humidity An unexposed luminescent sheet and an image-receiving sheet are overlapped, 2
The processing solution ks0.
Next, spread the processing liquid between the luminescent sheet and the image-receiving sheet by squeezing it with a developing roller so that it has a thickness of 0.04xx. The image-receiving sheet of the present invention separates from the image-receiving sheet after ≠0 seconds after development, and the presence or absence of white spots in the transferred image determines optical fog due to cracks in the back layer. It can be seen that not only is the value small, giving a desirable appearance close to a flat state, but also there is no fog due to cracks and the surface is clearly in a good condition.

EXAMPLES Image receiving sheets (2B) to (2B)' were prepared by sequentially depositing the following layers on a support polyethylene laminated paper. ()
The numerical value inside indicates the coating amount in 2/m2.

Image-receiving sheet (2) l) Neutralization layer; Cellulose acetate (acetylation degree J3) (6), methyl vinyl ether-maleic anhydride copolymer (≠), Uvitex OB (trade name of Ciba Geigy) (
0,0hiro) 2) Cationic polymer electrolyte layer Cellulose acetate (degree of acetate! IG%) (μ, 2), the following compound (J, /) 3) Neutralization timing layer Cellulose acetate (degree of acetate! !俤)[,-1),/-(4
-hexylcarbamoylphenyl)-2,3-dihydroimidazole-corchion (0,,0+) 4) Image-receiving layer Cellulose acetate (degree of acetylation!3) (/, ri, palladium sulfide (7,jX/(11') ), l-(≠-hexylcarbamoylphenyl)-2゜3-dihydroimidazole-
Apply corchion (O2O3) and then apply sodium hydroxide.

The surface was saponified using a saponification solution containing ot'4-methanol JOOul dissolved therein to form an image-receiving layer.

5) Release layer butyl methacrylate-acrylic acid copolymer (molar ratio l!: t, t) (0,03) Image receiving sheet (3) 1) Neutralization layer; ν loin on acetic acid (acetic acid degree 13% ) (t), methyl vinyl ether-maleic anhydride co-t7x form (4c), Uvitex DB (trade name of Ciba Geigy) (0,0≠)l-(≠-hexylcarbamoylphenyl)-2,3- Dihydroimidazole-corchion (0
,/2) Cationic polymer electrolyte layer Cellulose acetate (degree of acetylation≠6) (4', -2), following compound (2,/) x:y:z=,,t:≠7. j: μ7j3) Neutralized timing layer cellulose acetate (degree of acetylation jj%) (, A, J-) 4) Image receiving layer cellulose acetate (degree of acetylation j3 excellent) (/, j), palladium sulfide (7, jXlo' ), /-(4t-hexylcarbamoylphenyl)-λ.

3-dihydroimidazole-corchion (0°02)k
Sodium hydroxide after application? .

02 Prepare an image-receiving layer by saponifying the surface using a saponification solution dissolved in 300 ml of total methanol.

5) Peeling layer: Bunal methacrylate acrylic acid co'N (molar ratio iz'', ri (o, o3) Image receiving sheet (4) l) Neutralization layer: Cellulose acetate (degree of acetylation: 3%) ( t), methyl vinyl ether-maleic anhydride copolymer (≠), Uvitex OB (trade name of Ciba Geigy) (
0,0≠) 2) Cationic polymer electrolyte layer Cellulose acetate (degree of acetylation ≠ A4 (2, J-), the following compound (/, 2) x:y:z=j:Hiroshi7.!:Hiroshi7 .j 3) Neutralization timing layer cellulose acetate (acetylation degree series '%) (f, j)
, /-(≠-hexylcarbamoylphenyl)-λ, 3
-dihydroimidazole-λ-thione (0,01) 4) Image-receiving layer Cellulose acetate (degree of acetate 33%) (/, ri, sulfide) radium (7, jXIO), /- (≠-hexylcarbamoylphenyl) -2゜3-dihydroimidazole-corchion (0゜02) Ev was applied, followed by sodium hydroxide IJ umta.

Dissolve 01 in 300 ytl of methanol and saponify it from the surface using a saponification solution to form an image-receiving layer.

5) Release layer Butyl methacrylate-acrylic acid copolymer (molar ratio/j", rj) (0,03) Image receiving sheet (5) 1) Neutralization layer; Cellulose acetate (degree of acetylation j 3%) (j) , methyl vinyl ether-maleic anhydride copolymer (≠), Uvitex OB (trade name of Ciba Geigy) (
0,0≠), /-(≠-hexylcarbamoylphenyl]-2,3-dihydroimidazole-corchion (O,
/j) 2) Cationic polymer electrolyte layer cellulose acetate (1f acetate≠6%) (≠, 2), the following compound (2, /) x:y:z=, t:≠7. j:≠7. j3) Neutralized timing layer on acetic acid (acetic acid i to j%) (r, j) 4) Image receiving layer cellulose acetate (acetylation degree j3%) (/, t), palladium sulfide (r, txlo) , /-(Hexylcarbamoylphenyl)-2゜3-dihydroimidazole-λ-thione (0゜02) was applied, and then sodium hydroxide was applied.

The surface was saponified using a saponification solution containing 0fff methanol λroyttt and 20f glycerin VC to form an image-receiving layer.

5) Peeling layer Butyl methacrylate-acrylic acid copolymer (molar ratio/!:I) The image receiving sheet of Example 1 was placed on the back side of the image receiving sheets (2) to (5) of Riko et al. The same back layer as sheet/-7 was coated, and (λB) to (jB) were used.

Curl evaluation was performed on these image receiving sheets TF in the same manner as in Example 1, and the results are shown in Table 3.

(＼Effect of the invention) By providing a layer containing a cationic polymer electrolyte together with the image-receiving layer on the image-receiving layer side of the support, and using a specific amount of hydrophilic colloid on the side that does not have the image-receiving layer (back side). The anti-curl effect is significantly improved. This effect is even more remarkable when the back side does not contain a polyol containing two or more hydroxyl groups.

Claims (1)

[Claims] An image receiving element for a silver salt diffusion transfer method having an image receiving layer containing at least a silver precipitant on a support, and a layer containing a cationic polymer electrolyte between the support and the image receiving layer, the image receiving layer of the support. (1) a light-shielding layer containing a black pigment and a hydrophilic colloid; (2) a light-reflecting layer containing a white pigment and a hydrophilic colloid; The layer and/or the light reflecting layer contains spherical particles having a glass transition point (Tg) of 30°C or less, and the coating amount of hydrophilic colloid on the back side is 6 to 20 g/m^2. Image receiving element for silver salt diffusion transfer method.