JPH02211446A - Image receiving element of silver salt diffusion transfer method - Google Patents

Abstract

PURPOSE:To substantially prevent flawing of the surface of silver salt diffusion transfer images by using cellulose ester and a polymer having a residual group contg. an acid anhydride ring in a neutralization timing layer. CONSTITUTION:The image receiving layer is formed by successively laminating at least the alkali neutralization layer, the neutralization timing layer (A) and the image receiving layer contg. silver settling nuclei. Cellulose ester (A1) and the polymer (A2) having the residual group contg. an acid anhydride ring are incorporated in the layer A. Cellulose acetate, etc., are usable for the component A1 and copolymer of methyl vinyl ether and maleic anhydride, etc., are usable for the component A2, respectively. Further, 1-(4-hexylcarbamoylphenyl)-2,3- dihydroimidazole-2-thion, etc., can be added to the layer A.

Description

[Detailed description of the invention] (Industrial application field) This invention relates to silver salt diffusion transferable photographic elements.

More specifically, it relates to the image receiving element.

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

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

By the way, the basic layer structure of the image receiving element is, from the support side, an alkali neutralization layer containing an acidic polymer, a neutralization timing layer containing cellulose acetate as a main component, and an image receiving layer containing silver deposition nuclei. The layer can be obtained, for example, as follows.

That is, U.S. Pat. No. 3,179.517 describes saponifying an acetyl cellulose film with an alkali to form a layer of regenerated cellulose, and then immersing the regenerated cellulose layer in a gold salt solution and a reducing solution. A method is described in which the gold colloid is produced by reacting within the layer to form a silver deposition nucleus of the gold colloid. In addition, the special public service number 44-3275
In step 4, alkali-impermeable polymer material is impregnated with silver deposition nuclei by vacuum evaporation, then dissolved in a solvent that dissolves the polymer material, applied to a support, dried, and then coated with this polymer layer. A method is described in which the surface layer is made by saponifying it to make it permeable to alkali.

Furthermore, Japanese Patent Publication No. 46-43944 describes a method of forming silver precipitation nuclei in a solution of acetylcellulose, coating it on a support, and then saponifying the acetylcellulose to make regenerated cellulose. ing.

However, when obtaining regenerated cellulose by the above method,
The alkaline solution may penetrate to the lower neutralization timing layer and partially saponify the cellulose acetate that constitutes the core layer.Originally, it would be sufficient if only the image forming layer was saponified to form a cellulose film. If the lower neutralization timing layer is saponified for the reasons mentioned above, the photographic performance of the image-receiving element will change, leading to undesirable results. The alkaline processing liquid applied between the light-sensitive element and the image-receiving element is absorbed more by the image-receiving element, which may cause delays in image formation and may affect the storage stability of the formed image, i.e. discoloration when left in a bright or dark place. and greater fading. Also,
For the above-mentioned reasons, the drying of the image forming layer immediately after @M of the photosensitive element and the image receiving element is delayed, so that the surface of the layer is easily scratched, and in some cases, an undesirable failure such as partial loss of the image occurs.

In order to eliminate these disadvantages, it is preferable that the progress of the saponification reaction is shallow and that the progress of saponification to layers below the image forming layer is suppressed as much as possible.

(Problems to be solved by the invention) For the above purpose, Japanese Patent Application Laid-Open No. 63-47757,
No. 59, etc., describes a method for slowing down the progress of the saponification reaction.

However, even with these methods, the surface of the image forming layer may be easily scratched. In particular, when the separation was carried out under conditions of high relative humidity, there remained the problem that even if the saponification reaction was shallow, drying was delayed and the surface was easily scratched. Accompanying the saponification reaction, the acetylcellulose membrane contracts by releasing acetic acid. The interface between the saponified and non-saponified parts is strained due to shrinkage due to saponification.
It is thought that the more the interface between saponification and non-saponification becomes clearer, the more strain will be concentrated. It has become clear that due to this strain, the film can peel off at this interface under some conditions due to a slight external force.

(Objective of the Invention) An object of the present invention is to provide a silver salt diffusion transfer image receiving element that is resistant to scratches on the surface after peeling.

Still another object of the present invention is to provide a silver salt diffusion transfer image receiving element which has excellent image storage stability.

(Means for Solving the Problems) As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by the silver salt diffusion transfer method image receiving element described below.

A silver salt containing an image-receiving layer containing silver deposition nuclei in regenerated cellulose obtained by coating at least an alkali neutralization layer, a neutralization timing layer, and a cellulose ester on a support in order from the support side and then saponifying with an alkaline solution. A silver salt diffusion transfer imaging element, wherein the neutralizing timing layer comprises a polymer having a residue containing a cellulose ester and an acid anhydride ring.

By including a polymer having a residue containing an acid anhydride ring in the neutralization timing layer, the cellulose ester is saponified and contracts, causing distortion, while the acid anhydride ring opens and causes strain.
It is presumed that the desired effect appears because it acts in the direction of alleviating strain by being neutralized and hydrated.

The inclusion of cellulose ester and anhydride rings in the neutralization timing layer is disclosed in U.S. Pat. This is completely different from the structure saponified by alkaline solution in the silver salt diffusion transfer film unit of the present invention, and the effect is also different.

The polymer having an acid anhydride ring preferably has the following formula (%) where A represents an ethylenically unsaturated monomer residue having an acid anhydride ring, and B represents an ethylenically unsaturated monomer residue not containing the above ring represents.

X and 7 represent the copolymerization ratio of each residue of A and B, expressed in mol%, and X is from 20 to 100, preferably from 40 to 75.

Examples of the compound A include maleic anhydride and 3-methacryloyloxyethyloxycarbonylphthalic anhydride, with maleic anhydride being particularly preferred.

Monomers B include styrene, N-vinylpyrrolidone, alkyl vinyl ethers such as methyl vinyl ether, butyl vinyl ether, octyl vinyl ether,
Acrylic esters, methyl acrylate, methacrylic esters such as methyl methacrylate, acrylamides, methacrylamides, ethylene vinyl acetate, and the like. The monomer B may be one type or two or more types.

Examples of polymers made by polymerizing these are poly(styrene-co-maleic anhydride) (X/y-50150),
Poly (methyl vinyl ether co-maleic anhydride)
(x/y=50150), poly(acetic acid and maleic anhydride) (X/y-50150), poly(N-vinylpyrrolidone-maleic anhydride) (x
/y-50150), poly(butyl vinyl ether co-maleic anhydride) (X/3'-50150)
, poly(ethylene-co-maleic anhydride) (x/y
-50150), poly (methyl acrylate to koh maleic anhydride) (x/y -70/30), poly (methyl methacrylate to koh maleic anhydride) (x/y
y-75/CHl CH3 X/Y = 40/60 (mo
l/mol)x/y/z=35/45
/ 20 (mol/mol/mol) x / y = 30 / 70 (mol/mol
), but maleic anhydride copolymers are preferred, especially poly(ethylene-maleic anhydride).
, poly(methyl vinyl ether co-maleic anhydride) is particularly preferred.

These polymers having a residue containing an acid anhydride ring are known from US Pat. No. 4,009,030 and the like.

The amount of polymer having a residue containing an acid anhydride ring to be mixed in the neutralization timing layer cannot be generalized because the effect varies depending on the polymer used, saponification method 11 layer composition, treatment liquid formulation, etc. is 2 to 2 for cellulose ester.
3 Qwt%, preferably 4 to 25 wt%.

As the cellulose ester, acetylcellulose, cellulose propionate, cellulose acetate butyrate, cellulose acetate propionate, etc. are used, and acetylcellulose is preferred.

The amount of cellulose ester used as the neutralization timing layer varies depending on the degree of esterification, the type of ester, the type and mixing ratio of the polymer having a residue containing an acid anhydride ring, but is 1 to 15 g/resistant, Preferably 2-10
g/rd.

The neutralization timing layer is partially saponified, depending on the saponification method or layer structure, but e! Polymers having residues containing II anhydride rings may also undergo partial ring opening, neutralization, or partial esterification.

Further, the neutralization timing layer may contain silver deposition nuclei, which will be described later, in the same manner as the image receiving layer, as long as it substantially functions as a neutralization timing layer.

A preferred embodiment of the image-receiving layer constituting the image-receiving element of the present invention is that in the silver salt diffusion transfer method, a substance (referred to as a silver deposition nucleus substance or development nucleus) that catalyzes the reduction reaction of a water-soluble silver complex is treated with an alkaline treatment composition. A preferred method for obtaining an image-receiving layer, which is a layer contained in a material-permeable matrix material, includes:
First, a cellulose ester (preferably cellulose acetate) in which silver deposition nuclei are dispersed is applied, and then the above-mentioned alkaline solution is applied thereon, and as it dries, a saponification reaction on the surface proceeds, converting it into a regenerated cellulose membrane.

The alkaline compound used in the alkaline solution is preferably an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide. The solvent is preferably a lower alcohol, such as methanol or ethanol, and in some cases, water (by volume) is preferred. It is also effective to control the progress of the saponification reaction by mixing polyhydric alcohols or derivatives thereof as described in JP-A No. 63-47757, if necessary. be.

The matrix material permeable to the alkaline treatment composition is
As mentioned above, regenerated cellulose obtained by subjecting a cellulose acetate layer to an alkali saponification reaction is preferred.

Silver deposition nuclear materials 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 daughter deposition nuclei can be used. These silver deposition nuclei can be prepared by reducing the corresponding metal ions to form metal colloidal dispersions or by mixing metal ion solutions with soluble sulfide, selenide or telluride solutions to form water-insoluble metals. It is obtained by making a colloidal dispersion of sulfide, metal selenide or metal telluride.

To obtain an image-receiving element that gives a favorable tone image, these silver deposition nucleating materials are usually present in the image-receiving layer in concentrations of 1O-1e to 10-1e.
10-'g/ad, preferably 10-'' to 10-'g/ad
Include cll.

In a preferred embodiment, there is no extra-layer hydrophilic polymer layer containing regenerated cellulose as a main component between the neutralization timing layer and the image-receiving layer.

Diffusion transfer methods are currently well known in the art, and details thereof will be omitted. For more information, please contact A. Lott (A, R.
ott), E, Weyde, “Photographic Silver Defusion Transfer Process is PhotographicSi
lver Diffusion Transfer P
Focal.

Press+ London+/972; C.B. Neblett) (C, B, Neblett), 1
Handbook of Photography and Librography
hy and Rsprography)” Va
n No5trand Re1nhold 1st nhol
d 77), Chapter 12 One Step Photography (0ne-3top
Photography); Aist (Haist)
, Modern Photographic Processing (Mo
dern Photographic Process
ing)' Pol (Vol), 2, Chapter (Chap
ter) 8 Day Fusion Transfer (
Diffusion Transfer) etc.

Many types of photographic materials can be made using this diffusion transfer method. That is, a photosensitive material in which a silver halide photographic emulsion is coated on a support and an image-receiving material in which an image-receiving layer containing silver deposition nuclei is coated on another support are superimposed, and alkaline processing, which is a processing element, is carried out. It is known that a transferred silver image can be obtained by spreading a composition, for example a high viscosity or low viscosity alkaline processing composition comprising a developing agent and a silver halide solvent, between the two materials. , this photographic material is advantageously used in the practice of the present invention.

Another photographic material is U.S. Patent No. 2,861.8.
A photosensitive layer and an image-receiving layer as described in 85 are layered and coated on a single support, and the positive image can be observed through the negative image by utilizing the high covering power of the positive image. something is known.

Furthermore, as another photographic material, there is known a photographic material having the same structure as above, in which the layer of light-sensitive material is washed off after diffusion transfer processing, and only a positive image is obtained.

Furthermore, there are also known photographic materials in which the photosensitive layer and the image-receiving layer have an integrated laminated structure on the same support, and can be used without 'JIM'ing the photosensitive element and the image-receiving element after diffusion transfer processing. ing.

These various photographic materials are described in detail in the above-mentioned section.

The photosensitive element used in the present invention has a photosensitive layer containing one or more silver halide emulsions on a support. As the silver halide, highly sensitive silver iodobromide (iodine content: 3 to 10 mol %) is particularly preferred.

These can be dispersed in suitable protective colloidal substances such as gelatin, agar, albumin, casein, collodion, cellulose-type substances such as carboxymethyl cellulose, polymers such as polyvinyl alcohol or linear polyamides such as polyhexamethyleneazibyamide. . A suitable emulsion for use in overcasting is P. Grafkide (
P.

Written by Glafkides)
Photographic ink (Chigis et Physj
que Photographique) (Paul
Montel Publishing, 1976), Photography Ivy Emulsion Chemistry (Photog, F. Duffin)
rapicEmulSion Chemistry
) (The Focal Press, 1
(966), Bouy El Zelikman et al. (V, L.

Making and coating photographic emulsion (Ma
klngand Coating Photogr
aphic E+5ulsion) (The Fo
calPress, 1964).

These silver halide emulsions can be subjected to chemical sensitization, spectral sensitization, and superchromatic sensitization as required. Further, commonly known anti-capri agents, hardeners, development accelerators, surfactants, antistatic agents and the like can be included.

It is also useful to provide a protective layer on the photosensitive layer to protect the photosensitive layer from physical damage, and to add cloak agent particles to the protective layer to improve surface slipperiness and prevent adhesion. It is.

As the processing element used in the present invention, various processing compositions are used. Preferably, the processing composition contains a developing agent, a silver halide solvent, and an alkaline agent, depending on the purpose. , a developing agent and/or a silver halide solvent may also be included in the light-sensitive element and/or in the image-receiving element.

Suitable silver halide developers include benzene derivatives in which at least two hydroxyl and/or amino groups are substituted in the benzene nucleus (D-ortho or para position) such as hydroquinone, amitol, metol, glycine, p-aminophenol and pyrogallol; and hydroxylamines, especially primary and secondary aliphatic and aromatic N-substituted or β-hydroxylamines which are soluble in aqueous alkali, such as hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine. and Nidwin Ench Land, etc., W2,857,
276 and as described in Milton Green et al., US Pat. No. 3,293,034.

Hydroxylamine derivatives having a tetrahydrofurfuryl group described in JP-A-49-88521 may also be used.

In addition, amyl reductones described in West German Patent No. 111 (OLS) 2009054, 2009055 and 2009078, and U.S. Patent No. 4°128.425
Also used are the heterocyclic amyl reductones described in .

Additionally, tetraalkyl reductin acids described in US Pat. No. 3,615,440 can also be used.

Further, the above developer can be used in combination with the auxiliary developer such as a phenidone compound, a p-aminophenol compound, and ascorbic acid.

Suitable silver halide solvents include conventional fixing agents such as sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate and others described in the above-mentioned U.S. Pat. No. 2,543,181; and combinations of cyclic imides and nitrogen bases. such as those in which pulpyrate or uracil is combined with ammonia or amines and Nidwin Etch Land et al., U.S. Patent No. 2.85.
7.274 are included.

1,1-bissulfonyl alkanes and their derivatives are also known and can be used as silver halide solvents in the present invention.

The processing composition comprises an alkali, preferably an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide.The processing composition is distributed as a thin layer between the superposed photosensitive element and the image receiving element. Where applicable, the treatment composition preferably includes a polymeric film-forming agent, thickening agent or thickening agent.

Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful and are included in processing compositions in concentrations effective to provide suitable viscosity according to known principles of diffusion transfer photography. The processing composition may further contain other auxiliary agents known in the silver salt diffusion transfer process, such as antifoggants, toning agents (
toning agents), stabilizers, and the like.

The basic constituent layers of the image receiving element used in the present invention are an alkali neutralizing layer, a neutralizing timing layer, and an image receiving layer in order from the support side. It may also contain an iodide ion trapping layer or a delamination layer, and an element containing these layers is a desirable embodiment.

Further, another hydrophilic polymer layer may be provided between the image forming layer and the neutralization timing layer, if necessary. Polymers used in this hydrophilic polymer layer include, for example, gelatin, derivative gelatin (such as phthalated gelatin), I!* <for example, starch, galactomannan, gum arabic, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, pullulan,
hydrophilic synthetic polymers (eg, polyacrylamide, polymethylacrylamide, poly-N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, etc.).

The support constituting the image receiving element of the present invention may be a hard material such as glass or ceramics, or a flexible material such as paper or film, but in any case, during storage or processing, It is important to choose one that does not cause significant dimensional changes. Such supports may be transparent or opaque, such as polyester films, polycarbonate films, polystyrene films, films of cellulose derivatives, paper, baryta paper, pigment-coated paper such as titanium white, and the surface of paper coated with polyethylene, polystyrene, Examples include paper laminated with a polymer such as a cellulose derivative. The image receiving element of the present invention is generally in the form of a sheet cane using such a flexible material as a support.

It is preferable to use a film-forming acidic polymer for the neutralizing layer that can be used in the image-receiving element 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, and methyl vinyl ether copolymers.
Maleic anhydride copolymer, ethylene-maleic anhydride copolymer, monobutyl ester of copolymer of maleic anhydride and ethylene, monobutyl ester of copolymer of maleic anhydride and methyl vinyl ether, maleic anhydride and ethylene Monoethyl ester of a copolymer of , monopropyl ester of the same copolymer, monobenzyl ester of the same copolymer, monohexyl ester of the same copolymer, etc.; polyacrylic acid; polymethacrylic acid; copolymers of acrylic acid and methacrylic acid in various ratios ; various ratios of acrylic acid or methacrylic acid and other vinyl monomers, such as acrylic esters (such as butyl acrylate), methacrylic esters, vinyl ethers, acrylamides, methacrylamides, etc.;
Preferably the acrylic acid or methacrylic acid content is 50
~90 mol% copolymer, etc. can be used.

Among these acidic polymers, it is preferable to use polyacrylic acid or acrylic acid-butyl acrylate copolymer. The acidic polymers may be mixed with cellulose derivatives such as acetyl cellulose or other polymers for the purpose of increasing the .

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

Example 1 Formation of the image receiving sheet (1) The following layers were prepared in order on the support polyethylene laminate paper. The coating amount is shown in g/m.

1) Neutralization layer: Cellulose acetate (degree of acetylation 55%) (6), methyl vinyl ether-maleic anhydride copolymer (4), Uvitex OB (trade name of Ciba Geigy) (0,04) 2) Iodine ion trapping layer Cellulose acetate (degree of acetylation 46%) (4,2), the following compound (2,1) S:y:z feather 5:47. 5:47. 53) Neutralization timing layer: Cellulose acetate (degree of acetylation 55%) (8,5), 1-(4
-Hexylcarbamoylphenyl)-2,3-dihydroimidazole-2-thione (0,06) 4) Image-receiving layer: Cellulose acetate (degree of acetylation 53%) (1,5), palladium sulfide (7,5XIO-') , L-(4-hexylcarbamoylphenyl)-2゜3-dihydroimidazole-2-thione (0゜02) was applied, and then 12゜9g of potassium hydroxide was dissolved in methano-Jt;300- to make a saponified solution. The surface was saponified to form an image-receiving layer.

5) Release layer Nibutyl methacrylate-acrylic acid copolymer (molar ratio 15:85) (0,03) 2. Creation of image-receiving sheets (2), (3), (4), (5) Image-receiving sheet ( 3-2), 3-3), 3-4), 3-5, respectively, in place of the neutralization timing layer of layer 1) of layer 3).
), except that the image receiving sheets (2) and (3
), (4), and (5) were created.

3-2) Cellulose acetate (degree of acetylation 55.5%) (7,8
) Poly(methyl vinyl ether co-maleic anhydride)
(x/y-50150) (0,7) 1-(4-hexylcarbamoylphenyl)-2,3-dihydroimidazole-2-thione (0,06) 3-3) Cellulose acetate (degree of acetylation 5565%) (7,1
) Poly(methyl vinyl ether co-maleic anhydride)
(x/y=50150) (1,4) 1-(4-hexylcarbamoylphenyl)-2,3-dihydroimidazole-2-thione (0,06) 3-4) Cellulose acetate (degree of acetylation 55.5 %) (7,8
) Poly(ethylene-maleic anhydride (X/Y plot 50
150) (0,7) 1-(4-hexylcarbamoylphenyl)-2,3-
Dihydroimidazole-2-thione (0,06) 5) Cellulose acetate (degree of acetylation 55.5%) (7,8) Poly(methyl vinyl ether co-methyl monomaleate) (x/y-50150) (0° 1-(4
-hexylcarbamoylphenyl)-2,3-dihydroimidazole-2-thione (0,06) The following layers were deposited in sequence on a two-lambda support (black polyester film): 1) iodobromide 11 (iodine content 6.5
mol%) (1i amount 0.59g/n (>, gelatin (
3,5) 2) Protective layer Gelatin (0,7), polymethyl methacrylate particles (0,1) Kabuto Ml Kumaran crab potassium hydroxide (40% K O) l aqueous solution) Titanium dioxide hydroxyethyl cellulose Zinc oxide N, N -Bis-methoxyethylhydroxyamine triethanolamine solution 323 cc g 9g 9.75g 5g Table 1 The photosensitive sheet was left unexposed and the image-receiving sheet (11-
(5), and the processing liquid was spread between both sheets to a thickness of 40 μm for diffusion transfer development.

Both sheets were peeled off after 30 seconds in an atmosphere of 25° C. and 80% RH to obtain a solid black image. Ball diameter 0.5 after peeling #11 minutes
- Applying a load of 300 g to a ballpoint pen, 31 squares were drawn on the surface of the peeled image-receiving sheet to examine the degree of damage to the film.

The results are shown in Table 1. It can be seen that the image receiving sheet according to the present invention has strong adhesion immediately after peeling.

(Effect of the invention) As claimed in the claims, since the neutralization timing layer contains a polymer, preferably a copolymer, having a residue containing a cellulose ester and an acid anhydride ring, the surface after peeling is less likely to be damaged. , the silver salt diffusion transfer image is changed.

Claims (1)

[Claims] A silver salt containing an image-receiving layer containing silver deposition nuclei in regenerated cellulose obtained by coating at least an alkali neutralization layer, a neutralization timing layer, and a cellulose ester on a support in order from the support side and then saponifying with an alkaline solution. A silver salt diffusion transfer imaging element, wherein the neutralizing timing layer comprises a polymer having a residue containing a cellulose ester and an acid anhydride ring.