JPS6037553A - Image receiving element for silver salt diffusion transfer process - Google Patents

Abstract

PURPOSE:To stabilize a silve image formed by a diffusion transfer process and to prevent reduction in the performance of an image receiving element during storage before development by incorporating a specified compound. CONSTITUTION:A compound represented by the formula is incorporated into an image receiving element so that it is contained in a layer other than a layer contg. silver depositing nuclei. The compound is decomposed with alkali in a developing soln. during development to produce a diffusible mercapto compound which acts to prevent the fading of a silver image, so the silver image can be held well. Since the diffusible mercapto compound is not present during storage before development, the performance of the image receiving element is not reduced. Thus, a silver image is effectively stabilized, and the undeveloped image receiving element undergoes no reduction in the performance during storage. In the formula, each of R<1> and R<2> is H, <=8C alkyl or the like; each of G<1> and G<2> is <=30C alkoxy; X is O, S or NR<5>; R<5> is <=20C alkyl or the like; and each of R<3> and R<4> is <=10C alkyl or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photographic elements for use in silver salt diffusion transfer processes.

Conventionally, 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 an image-receiving element containing silver precipitation nuclei are superimposed, and a film is formed between these two elements in the presence of a GL image agent. A known method is to obtain a positive silver image directly on an image-receiving element by applying an alkaline processing solution containing a silver halide solvent to the image-receiving element.

In this method, the unexposed silver halide emulsion in the 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 the image-receiving element. A positive image is directly formed by precipitation as a silver image due to the action of silver precipitation nuclei.

The image receiving elements used in this method are usually baryta paper,
Gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, regenerated cellulose, polyhinyl alcohol, alginic acid on a paper support such as polyethylene laminate paper, lacquer paper, synthetic paper, or on a film support such as acetyl cellulose, polyethylene terephthalate, polystyrene. Nickel sulfide, silver sulfide,
Metal sulfides such as palladium sulfide, or gold, silver,
It is made by providing an image receiving layer containing silver precipitation nuclei selected from noble metal colloids such as palladium.

Many inventions have been made and patent applications have been filed to improve these image receiving elements. Among these methods, a method is known in which regenerated cellulose is used as a binder in the image-receiving layer.

Specifically, U.S. Pat. A method is described for making an image-receiving element by reacting gold colloids in that layer to form silver precipitation nuclei. In addition, in Tokuko Sho-Mari-327111, silver precipitation nuclei are formed on an alkali-impermeable polymer material by vacuum deposition, then dissolved in a solvent that dissolves the polymer material, coated on a support, and dried. Later, an image receiving element prepared by hydrolyzing the surface layer of this polymer layer to make it permeable to alkali is described.

Furthermore, in the case of Special Publication Akihiro A-1132, silver precipitation nuclei were formed in a solution of acetylcellulose, coated on a support, and then the acetylcellulose was hydrolyzed to form regenerated cellulose. Describes how to create elements.

Furthermore, Japanese Patent Publication Shoji-+2≠// describes an image-receiving element prepared by hydrolyzing a cellulose ester layer and incorporating silver precipitation nuclei into the hydrolyzed 1@ at the same time or after the hydrolysis. ing.

Additionally, U.S. Patent e, tt3. No. 1, No. 1, pp. 10-12, describes an image-receiving element prepared by hydrolyzing acetylcellulose with an acid in a solution to convert it into acetylcellulose with a low degree of acetylation, and coating it on a support.

However, silver images formed on image-receiving elements viewed in this manner have the drawback of being susceptible to discoloration or fading during storage.

j − As a way to improve this shortcoming, what is the special public interest rate of 163? ,
2, U.S. Patent J, 333.7f and British Patent/
, /A≠, and t≠2 each describe a method of applying a water-soluble polymer solution containing an alkali neutralizing component to the surface of the observed silver image.

However, with this method, it takes a considerable amount of time for the surface coated with the aqueous polymer solution to dry completely, and during this time, the surface is sticky and sticky, making it impossible to print overlapping prints, and fingerprints and dust can be removed. It was often attached. Further, it is troublesome to further apply such a liquid to a silver image.

In the specification of Japanese Patent Publication No. 5 T-QTTAIR, on the support,
(■) a hydrolyzable cellulose ester, polyvinyl ester or polyvinyl acetal layer containing compounds that are diffusible and capable of altering the properties of the silver image and which become permeable to alkali upon hydrolysis, and (It) silver precipitation nuclei thereon; An image receiving element is disclosed which is provided with a regenerated cellulose layer containing.

and a compound that can be diffused and changes the properties of the silver image.
- Organic mercapto compounds are described as compounds.

At this time, the diffusion transfer treatment liquid and one layer of mercapto compound gradually diffuse into ■1-, and the mercapto compound formed in U/- is uni1. It has the effect of preserving m and preventing discoloration and fading.

In order to fully exhibit the effect of preventing IF from discoloration and fading, it is necessary that the mercapto compound has sufficient ability to prevent discoloration and fading, and that the mercapto compound must have sufficient ability to prevent discoloration and fading while the undeveloped image-receiving element is stored and during diffusion transfer. During processing, it remains in one layer and after the diffusion transfer process creates the silver image, from layer 1 to n.
It is necessary to penetrate the layers and protect the image f# generated in the n layer. If diffusion of the mercapto compound from one layer to the n layer occurs before the diffusion transfer process is completely completed, development will be inhibited and the optical density of the transferred silver image on the receiver element will be reduced overall. Furthermore, if the diffusion of the mercapto compound is too slow, discoloration or fading of the silver image may occur before the mercapto compound can strengthen the silver image.

However, the mercapto compounds described in Japanese Patent Publication No. 1987-17-G V Guit are insufficient in their ability to prevent discoloration or fading, causing discoloration or fading of images, and moreover, while undeveloped image-receiving elements are stored. Develop by spreading from 1st layer to 1st layer.
f:1j1]! (1) It had the disadvantage of lowering the optical density of the transferred silver image.

In addition, JP-A-12-07JF discloses an image-receiving element prepared by using homopolymers, copolymers, and graft polymers of monoacrylates or monomethacrylates of polyhydric alcohols as a polymer layer containing a compound that changes the properties of a silver image. It is written about.

However, JP-A-Sho Litter lλ01. Similar to the compounds described in Japanese Patent Publication No. JT-1eg/g, the compounds described in JP-A JT-1eg/g do not sufficiently prevent discoloration or fading of images, or preserve undeveloped image-receiving elements. Meanwhile, there was a drawback that the optical density of the transferred silver image was reduced.

Furthermore, British Patent/27t/A/2-mercapto-/ for obtaining stable silver images by diffusion transfer method.

3, the use of ≠-triazole derivatives is disclosed. Also, in the US patent JtjjJIO, j-seleno-
/, 2, 3. It is disclosed that II-tetrazole derivatives can not only improve the tone of silver images obtained by diffusion transfer to medium gray, but also provide stable silver UMJ images.

However, these compounds have the disadvantage that the effect of stabilizing the silver image obtained by the diffusion transfer method is insufficient, and that discoloration or fading of the image occurs. Furthermore, there is a need for a compound and an image-receiving element that are highly effective in stabilizing silver images and do not cause any deterioration in the performance of the undeveloped image-receiving element during storage.

Accordingly, the seventh purpose of the present invention is to provide a novel image-receiving element for diffusion transfer, and second, to provide a novel image-receiving element for diffusion transfer that does not change in performance during storage before development. Third, it is to provide an image receiving element in which silver images obtained by diffusion transfer are stable;
It is an object of the present invention to provide a novel image stabilizer that is f-effective and at the same time does not significantly reduce the performance of an image-receiving element during storage before processing.

As a result of various studies, the inventors of the present invention found that the above-mentioned object can be achieved by using an image-receiving element containing a compound represented by the following general formula CI).

General formula (I): 10- Next, specific examples of the compound of the present invention represented by general formula (I) will be shown, but the scope of the present invention is not limited thereto.

(l (J Hiroshi -l　3　- (J 0 /, 2 -/4Z- /3 0 1 hiro l-yo /l 7 /l.

Part j- 9 20゜f KoJ -77- 76- 3 2'A +2Jnee/I- 7 0 L Kota The compound represented by the general formula ([) is a heterocyclic compound represented by the general formula (''). It can be synthesized by mixing a methylene malonic acid ester represented by the general formula (III) in an appropriate organic solvent.

General formula (1) [wherein, This is the same as the explanation in .] As the reaction solvent, alcohols such as methanol and ethanol, aprotic polar solvents such as acetonitrile and NlN-dimethylformamide, and carboxylic acids such as acetic acid can be used. When a mixed solvent with other solvents is used, the production rate of the compound represented by the general formula CI) is high and favorable results are obtained.The reaction proceeds at room temperature, but may be heated to 00C to 100C. A base such as sodium acetate, sodium methoxide, or triethylamine may be added.

The compound represented by the general formula (I) is prepared by combining the compound represented by the general formula (T) with a large excess of alcohol in the presence of a catalyst such as sulfuric acid, radruene sulfonic acid, tetracytoxytitanium, etc. It can also be synthesized by replacing the alkoxy groups G1 and G2 in general formula (1) with other alkoxy groups by a so-called transesterification reaction. An example of this method is, for example, Niss Arsandra Dougrie Caro S, R1, 8an
Written by dler and W, Karo - Ko/- Published in 2007, pages 3 to 2! stated on the page.

Next, the method for synthesizing the compound of the present invention will be explained by giving a synthesis example.

Synthesis Example 1 The method described in Synthesis of Compound I Volume sty page (/I# published in 2013),
That is, l-phenyl-λ obtained by heating and refluxing an adduct of phenyl thiocyanate and aminoacetaldehyde diethyl acetal in 30% sulfuric acid.
- mercaptoimidazole or l-phenyl-u,
j-dihydroimidazole-2-thionecof with acetonitrile 3 ml / John Wlley & 5ons
Diethyl methylenemalonate 2f, which was synthesized by the method described on page 121 of 1263, published by Co., Ltd., was added and stirred for 30 minutes. During this time, the reaction proceeded exothermically. Thereafter, the reaction mixture was poured into 10 liters of water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was dissolved in a mixture of hexane and inpropyl alcohol, and then cooled to obtain crystals of Compound 1. Revenue! /,
4'+1 Synthesis Example 2 Synthesis of Compound 31/If, jg of stearyl alcohol and 0.0g of tetrabutoxytitanium. If was added, and the mixture was stirred on a steam path under reduced pressure for 5 hours. After cooling the reaction solution, it was purified by silica gel column chromatography to obtain compound 31 of 230machi.
I got it.

Synthesis Example 3 Synthesis of Compound 21 Compound 2≠ was obtained in exactly the same manner as in Synthesis Example 2 except that octyl alcohol JP was used instead of stearyl alcohol Ill. Yield: ■Synthesis Example 4 Synthesis of compound aminoacetaldehyde diethyl acetal 2/, 7
269 parafluorophenyl isothiocyanate was added to a solution consisting of 9 and Omt of carbon tetrachloride at a liquid temperature of 300C.
The mixture was added while maintaining the temperature below, and then stirred at room temperature for 2 hours. Carbon tetrachloride was distilled off under reduced pressure.
mt was added and heated under reflux for 30 minutes. Cooling drain water J 00
M/ was added, and the precipitated crystals were separated and washed with water. The crystals were recrystallized from isopropyl alcohol and then from ethanol to give /-(≠-fluorophenyl)-2-mercaptoimidazole, i.e. l-(≠-fluorophenyl)-2.
, 3-dihydroimidazole-2-thione O1 and 3-dihydroimidazole-2-thione. 2 g of this compound was dissolved in a mixed solution of 30 M of acetonitrile and 10 parts of acetic acid, and 2 f of diethyl methylenemalonate was added thereto and stirred for 30 minutes. During this time, the reaction proceeded exothermically. Thereafter, the reaction mixture was poured into water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was dissolved in a mixture of hexane and isopropyl alcohol, and then cooled to obtain crystals of the compound≠. Shufir/, JQ synthesis example 5
Octyl alcohol jf and tetracytoxytitanium o, iy were added to the synthetic compound of compound 23, 44 /f/, and the mixture was stirred on a steam bath under reduced pressure for 5 hours. After cooling the reaction solution, it was purified by silica gel column chromatography to obtain 2.210q of Compound 23.

Synthesis Example 6 Synthesis of Compound-27 Compound 27 (273q) was obtained in exactly the same manner as in Synthesis Example j except that octyl alcohol jf (stearyl alcohol jff was used instead of D).

It was synthesized from para-amino-7 benzoethyl ethyl acetate according to the method described in 1996, published on pages 31 to 3/j. 13 g of acetal was added dropwise over 5 minutes. The mixture was then stirred at room temperature for 1 hour. Carbon tetrachloride in the reaction mixture
Owl was added, the precipitated crystals were counted, and carbon tetrachloride jOw
27. By washing with T and drying. If N-(≠
-N'-C-2-ethoxyethyl) diourea was obtained. This compound ++h ioy
1100M1 of 30-thiosulfuric acid was added to the mixture and the mixture was heated at a high speed for 1 hour.

Reaction mixture was cooled to room temperature and drained 1. o.

ml was added and cooled on ice. Collect the precipitated crystals and add water λ0
Wash with θxtt, iaflovir alcohol lθOIMl', and hexane lθOwt in the order of 4(,S'l/(7
)/-(≠-carboxyphenyl)-2-mercaptoimidazolet'ibl-('I-carboxyphenyl)-co,3-dihydroimidazole-corchion was obtained. This compound, 2Jyp&iN, was cooled in N-dimethylformamide λθOwrl, and the liquid temperature was -jo to -7.
r0cKh was rejected. Add 1 isobutyl chloroformate to this solution.
53 ml of the solution was added dropwise while maintaining the liquid temperature between 1.0 Qc and -1 s'C. Then triethylamine/7.
After adding the liquid dropwise while maintaining the liquid temperature within the range of -j0C to -/s0C, stirring was continued for 70 minutes. Hexylamine t-2,op was added dropwise while maintaining the liquid temperature in the range of -j0C to -100C, and the mixture was continuously stirred for 30 minutes. Next, the mixture was stirred at room temperature for 2 hours, and sodium bicarbonate was dissolved in 11 parts of water and added thereto, and the precipitated crystals were collected and washed with water. The crude crystals were mixed with 2 parts of methanol and water (
Volume ratio) Recrystallize from the mixture and then dry to +20. Rif
/-(F-hexylcarbamoylphenyl)-comelcabutoimidazole-j-st)thi/-(4'-hexylcarbamoylphenyl),co,3-dihydroimidazole-2-thione was obtained. This compound/f was dissolved in a mixed solution of 30 ml of acetonitrile and vinegar m/Ome, and 2 g of diethyl methylene matetraphosphate was added thereto and stirred for 30 minutes. The reaction mixture was then poured into 1091 ml of water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and then the solvent was distilled off. After dissolving the residue in a mixture of hexane and isopropyl alcohol and cooling, 12 g of compound 7
Crystals were obtained.

Synthesis Example 8 Synthesis of Compound λ Octyl alcohol 71 and f-trabutoxytitanium o and iy were added to compound vy7/I/ and heated on a steam path under reduced pressure for 5 hours. The reaction mixture was purified by silica gel column chromatography to obtain the compound 32Owy.

Synthesis Example 9 Synthesis of Compound λt Compound-2t of 3ytxry was obtained in exactly the same manner as in Synthesis Example t except that 7g of stearyl alcohol was used instead of 7f/g of octyl alcohol.

The elemental analysis values of the synthesized compounds are shown in the table.

Table: Elemental Analysis Results The image forming method using Kotar silver diffusion transfer method is well known in the art, and its details can be found in, for example, A. Ro.
tt, B. Weyde “Photograp
hicSilver Diffusion Trans
fer Process”, Focal Press (
Published in 1972; “Ha
ndbook of Photography and
"Reprography" 7th edition, Chapter 1.2; Ha
by ist “Modern PhotographicP
"Rocessing" Volume 2, Chapter 2.

These documents describe various photographic materials used in the silver diffusion transfer method, but the compound of the present invention represented by the above general formula (I) is different from the one containing silver precipitated nuclei in the image-receiving element. By being included in a separate layer, the silver image obtained by the development process is prevented from fading, and at the same time, sufficient optical density can be obtained by development without deteriorating the performance of the image receiving element even during the storage period before development. It has been found that the object of the invention '5r of making it possible to form a silver image having: The cause of this favorable effect is −30
- The compound represented by the above general formula (I) is decomposed by the alkali in the developer solution during the development process to produce a mercapto compound that is diffusible and has an anti-fading effect on silver images; This is thought to be due to the absence of a diffusible mercapto compound that has an inhibitory effect.

The present invention is useful in various photographic materials used in the above-mentioned silver diffusion transfer method, but the present invention can be particularly effectively applied to materials in which a light-sensitive element and an image-receiving element are coated on separate supports. Embodiments of the present invention will be described in detail.

The photosensitive layer used in the present invention may contain one or more silver halides, examples of which include silver chloride, silver bromide and silver iodide, or mixtures thereof. silver chlorobromide, silver chloroiodobromide and silver iodobromide, which are combined with suitable protective colloidal substances such as gelatin,
Agar, albumin, casein, collodion, cellulose-type materials such as carboxymethyl cellulose, dispersed in vinyl polymers such as polyvinyl alcohol or flocculent polyamides such as polyhexamethyleneazibyamide. Emulsions suitable for such applications include P, Glaf
kids Written by Chimie etPhysique
Photography (Paul Montel)
Publishing, 1967), Pho by G. F. Duffin
tographic Emulsion Chemises
try (The Focal Press, /91.
(year), V. L., Zelikman et al. Ma.
King and Coating Photograp
hic Emulsion (The Focal Pr.
It can be produced by using the method described in ESS, 2013, p.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method of forming particles under an excess of gold and silver ions (so-called back mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

The silver halide emulsion may be a so-called primitive emulsion which is not chemically sensitized, but it is usually chemically sensitized. For chemical sensitization, the Glafkides, Duffin and 7, ell
Ikman et al.'s books or Grundlagen der Photography edited by H. Frleser
ischenProzessemit 8i1berh
alogenid-emulsionen (Akad
emischeVerlagese5chaft,
/91rr) can be used.

Silver halide emulsions can be spectral sensitized or superchromically sensitized, if necessary, by using cyanine dyes such as 7-anine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. can.

These color sensitization techniques have been known for a long time, for example, in US Pat.

1 3.7 dag, 4 λ, j/ri, ooi, 2, 77, 22, 3,4c10. '1311, -3
3 = 3.672. Zari No. 7, 3.70.3.377,
λ, trr, rus, 2, 9/2, 3λ ri,
3,397.0 Otsu O, 3. t/j.

No. 13j, same 3. t2za, ri t≠ issue, UK time jf/.

/91,302%, same/, No. 2112.311, same l
1.2ri3. ♂t2-, West German patent application (OLS)
Ko, 03θ, J2A, same 2. /21,710, Tokuko Shosu 3-≠ri 3, Mawariri l≠030, same ≠3-
No. 10773, U.S. Pat. No. 31//1.

No. 441, J, J', 2.2.0!2, No. 3, 5
27゜A4Z/No. 3. t/j, t/3, same J, 4
/j, l, No. 32, No. 3, 4/7, 225, No. 3゜4
3j, No. 721, No. 3,6 1it, No. 2/7, British Patent No. 37.110, No. 37.110, No. 37.110, No. 3, No. 721, No. 3,6 1it, No. 2/7, No. 37.110, No. 3, No. 3, No. 721, No. 3, No. 721, No. 3, No. 721, No. 3, No. 3, No. 721, No. 3, No. 721, No. 3, No. 3, No. 721, No. 3, No. 721, No. 3, No. 721, No. 3, No. 721, No. 3, No. 3, No. 721, No. 3, No. 721, British Patent No. 3, No. 37.
There is a description in the issue etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

Silver halide emulsions may contain coating aids. As the coating aid, those described in [coating-3≠-aidsJO] of Product Licensing Index, Volume 2, page 101 may be used.

Silver halide photographic emulsions may also contain antistatic agents, plasticizers, fluorescent brighteners, air antifoggants, and the like.

The silver halogenide emulsion used in the present invention has the Product Licensing Index, Vol.
Use the vehicle described in otsada's ``Vehicles'' section J (December 1971).

The silver halide emulsion is coated on a support along with other photographic layers if necessary. The application method is described in Product Licensing Index, Volume 22, 10 Risada's "coati".
The method described in ng procedures J can be used. The support is also available from Product Licensing Index, Volume 22, page 101 [5uppor
Those described in the section of tsJ can be used.

The photographic emulsion of the present invention has an increased sensitivity of 1f, increased contrast,
Or for the purpose of accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc. May include. For example, the US time ♂ "λ, go θ, No. 532, 2.11
23, tt No. 2,716.061, 3.4
77゜2&'0 No. 3.77.2,021, No. 3.
1Or, Oθ3, etc. can be used.

The photographic material produced according to the present invention may contain a water-soluble dye in the photographic emulsion layer or other hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, merocyanine dyes such as oxonol dyes and hemioxonol dyes are useful. Dyes may be mordanted in certain layers by cationic polymers such as dialkylaminoalkyl acrylates.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may also be mordanted with cationic polymers. For example, UK patent t13.171, US patent 2
, No. 171, 314, the same, Za3ri, ≠ No. 01, the same,
No. 112.157, 3. oar, 4cza No. 7, same! ,
No. 1111.309, 3. Dada J, No. 23, West Germany%
Liver Application (OLS)/, ri111. JA Ko-go, JP-A-5o
-41'7GJ1, 10-7/, 332, etc. can be used.

The processing composition used in the present invention contains a developing agent, a silver halide solvent, and an alkaline agent. Alternatively, it can be included in the image receiving element.

Suitable silver halide developers include benzene derivatives in which at least one hydroxyl and/or amide group is substituted in the ortho or para position of the benzene nucleus, 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- /9 of ethyl hydroxylamine and Nidowin Etchland etc.
U.S. Pat.
Included are N-alkoxyalkyl-substituted hydroxylamines such as those described in .

Also, Tokukai Sho≠2-1#,! Hydroxylamine derivatives having a tetrahydrofurfuryl group as described in r21 can also be used.

In addition, West German patent application (OLS) 2ooyor≠, λ
The amyl reductones described in θ0 and 071 and the heterocyclic amyl reductones described in US Pat.

Furthermore, the tetraalkyl reductin acids described in US Pat. No. 34/j≠3 can also be used.

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

Suitable silver halide solvents include conventional fixing agents such as sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate and others mentioned in US Pat. ; and combinations of cyclic imides and nitrogen bases, such as pulpyrate or uracil in combination with ammonia or amines, and Nidwin etch land, etc.! lr year 1
Combinations such as those described in U.S. Pat.

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

The treatment composition contains an alkali, preferably an alkaline hydroxide, such as sodium hydroxide or potassium hydroxide. If this is applied by distributing the processing composition as a thin layer between a superimposed photosensitive element and an image-receiving element, and especially if these elements are distributed in a superimposed relationship, the processing Preferably, the composition includes a polymeric film former, thickener or thickener. Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful for this purpose and are included in the processing composition in concentrations effective to provide adequate viscosity according to known principles of diffusion transfer photography. The processing compositions may also contain other auxiliaries known in the art of silver transfer, such as antifoggants, toning agents, stabilizers, and the like.

Mercapto compounds, imidazole compounds, indazole compounds, triazole compounds, etc. are useful as antifoggants and color toning agents, and are particularly described in U.S. Pat.
ft12jr, 3411+2gua 3, British patent //2
2/! r and West German patent application (OL8) / r o
u J A sfx To-C "At1-tail compound is effective. Also, when an oxyethylamino compound such as triethanolamine is included as a stabilizer, it is effective as described by Sidney Kasman (8idney Kasm.
an ) U.S. Patent 37. It has been found to be useful in increasing the shelf life of treatment compositions as described in No. 1gj.

As mentioned above, the image receiving element used in the present invention consists of a support carrying an image receiving layer containing a silver precipitant in a hydrophilic polymer binder.

Many examples of hydrophilic polymers are known, but as mentioned above, regenerated cellulose is particularly good.

Such an image-receiving element can be prepared by impregnating a cellulose ester, such as cellulose diacetate, with an iron precipitant by vapor deposition, then coating it on a support and alkaline hydrolysis, or by preparing it in a cellulose ester solution. For example, a method in which a silver precipitant is prepared on the spot by reacting iron nitrate and sodium sulfide, and then applied on a support and then subjected to alkali hydrolysis. A method in which a silver precipitant is embedded in a hydrolyzed layer at the same time as the cellulose ester layer is decomposed, and a method in which a silver precipitant is embedded in a layer that is hydrolyzed at the same time as the cellulose ester layer is hydrolyzed with alkali to produce regenerated cellulose, and then a silver precipitant is added in the hydrolyzed layer with, for example, chloroauric acid. All methods can be used, including the method of creating a silver precipitant by reacting with a reducing agent.

If necessary, a layer of partially hydrolyzed cellulose ester is left below the layer of hydrolyzed cellulose ester containing a silver precipitant. It is also possible to provide a polymer layer such as polyvinyl butyral.

These polymer layers are known to serve as waterproof 1m.

``Also, if necessary, a hydrophilic layer may be formed between the hydrolyzed cellulose ester containing a silver precipitant and the lower layer of cellulose ester, partially hydrolyzed cellulose ester, polyvinyl butyral, etc. Polymer layers with different properties may be provided. Examples of polymers used in this hydrophilic polymer layer include gelatin,
Sieve conductor gelatin (e.g. phthalated gelatin), sugars (e.g. starch, galactomannan, gum arabic, hydroxyethylcellulose, methylcellulose,
hydrophilic synthetic polymers (eg, polyacrylamide, polymethylacrylamide, poly-N-vinylpyrrolidone, co-hydroxyethyl methacrylate, etc.).

Furthermore, an alkali neutralizing agent layer may be provided if necessary. For example, in this alkali neutralizing agent layer,
The polymer acids described in Section 7 and the like are used.

Furthermore, 1- of a hydrophilic polymer such as carboxymethyl cellulose, gelatin, gum arabic, dimethylhydantoin-formaldehyde condensate, cellulose acetate hydrogen phthalate, etc. is added to -H in the image-receiving layer for the purpose of improving the releasability of the processing solution. Coating is also effective.

Furthermore, a fluorescent brightener can be added to improve the whiteness, and a plasticizer can also be added to soften the coated polymer layer.

In order to incorporate the compounds of the present invention into the image receiving element, they can be incorporated into one or more of the layers mentioned above.

In a particularly useful embodiment, U.S. Pat.
The image stabilizer of the present invention is added to the unhydrolyzed cellulose ester layer under the image-receiving layer containing the silver precipitant as described in the above. Alternatively, a layer of a hydrophilic polymer such as TidKλ-hydroxyethyl methacrylate is provided as a layer of hydrolyzed retacellulose ester as described in JP-A-2010-341; It has been found to be advantageous to add inventive image stabilizers.

The amount added to the cellulose ester layer, hydrophilic polymer layer, or other layer that has not undergone hydrolysis is approximately /-1000 x 10' m o I/m.
is preferred. Particularly preferred is 10~jOO×10−
The amount is 6m01/m2.

For incorporating the compounds of this invention into photographic elements, water or low boiling organic solvents such as methanol, ethanol, furonol, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, petroleum ether, benzene, toluene, They can be applied by dissolving them in ether, tetrahydrofuran, dioxane, dimethylformamide, ethyl acetate, butyl acetate, etc. with a suitable polymer, or they can be added to a solution of an image stabilizer after the photographic element has been prepared. They can also be incorporated by dipping the photographic element.

Examples of suitable silver precipitants include heavy metals such as iron, lead,
Zinc, nickel, cadmium, tin, chromium, copper, cobalt, especially noble metals such as gold, silver, platinum and palladium. Other useful silver precipitants are heavy metal sulfides and selenides, especially mercury, cartwheel aluminum,! Ilj
Mention may be made of the sulphides of lead, cadmium, cobalt, nickel, scissors, palladium, lead, antimony, bismuth, cerium and magnesium, and the selenides of lead, zinc, antimony and nickel. The function of materials such as silver precipitants in the silver transfer method is described, for example, in Nidwin H. Rand et al.

As is known in the art, a very small amount of the silver precipitant Fi is present, for example about 2 s.times.10" moI/m@2.

Usually use the lowest level possible, but higher Y
At 1k degrees, excessive silver is deposited or undesirable background density (density) occurs in highlight areas.
This is because it may occur. Mixed silver precipitants may also be used. It is thus possible to state that the image-receiving layer is substantially colorless and substantially transparent as far as the presence of precipitated nuclei is concerned.

Example 1 (1) Adjustment of image-receiving element (A) Polyethylene laminate paper obtained by corona discharge treatment of polyethylene (square meter: iroy 7 m2, thickness of polyethylene: 20 mm)
μm) on top of cellulose diacetate (degree of acetylation j′$
1) A solution of copolymer 7cof and methyl vinyl nitrate maleic anhydride dissolved in acetone copolymer 00111 was applied. The amount of polymer applied was zf/m 2 .

On top of this layer, a solution of cellulose diacetate 20f dissolved in acetone powder (and methanol 20@l) was coated. An image stabilizer as described below was added to this solution.Amount of cellulose acetate coated is 99
It was 7m.

The image stabilizers used are as follows.

Image-receiving element A-/Compound 7 (Present invention) Image-receiving element-
1 Compound θ (Invention) Image receiving element A-J Compound-2
4t (Present invention) Image-receiving element A-q Compound l (Present invention) Image-receiving element A-1/-Phenylucome (Comparative example)
Captoimidazole image-receiving element A-j No cooling (Comparative example) On top of this layer, cellulose diacetate log was further added in acetone r.
A solution dissolved in ooglt was applied. The applied cellulose diacetate was 3 f/m 2 .

A polyethylene laminate paper containing cellulose diacetate I- prepared in this manner was coated with an alkaline hydrolyzate containing a chain-destroying agent as shown below at 30 w/m.
An image receiving sheet A-/-2 for the diffusion transfer method was prepared by coating.

The alkaline hydrolyzate used was prepared as follows.

First, nickel nitrate θ, 7f was dissolved in 7 cc of water, and this was added to 1 oof glycerin. A solution prepared by dissolving sodium sulfide zg in water rcc was added to this solution with vigorous stirring to prepare a silver precipitation core dispersion of nickel sulfide.

To a solution prepared by dissolving sodium hydroxide zrg in J 00 ml of water and methanol/co 00 ml, the above-mentioned silver precipitation nucleus dispersion was added.

(2) Preparation of photosensitive layer sheet A gelatin-dispersed silver iodobromide emulsion having an average grain size of 1.0 μm was prepared by a conventional method. Take this in a 100f pot, j
It was dissolved in a constant temperature pass of OoC. 3-15 to this
-chloroco-[coethyl-5-(j-ethyl-λ-
penzothiasolonylidene) propenylcou 3-benzoxasilyl primary propane sulfonate, ter(λ-[3-
Ethylbenzothiazoline-koylidene)-2-methyl-/-propenyl]-3-penzothiasoliol propanesulfonate, ≠-hydroxy-6-methyA/-1,3
, 3a, 7-chitrazaindene aqueous solution 101
111. Hydroxy≠, 6-dichlorotriazine sodium salt / intussusception / O
wK Furthermore, 1 of sodium dodecylbenzenesulfonate
A 1% aqueous solution lOwIt was added and stirred.

This finished emulsion was applied to an undercoated polyethylene terephthalate φ film base containing titanium oxide to a dry film thickness of 5.
A sample was obtained by coating and drying to a micron size. The coated silver 1 was i,oy7nt.

(3) Treatment liquid composition Potassium hydroxide (3% KOf-1 aqueous solution) 3-23 cc Titanium dioxide 3f Hydroxyethylcellulose 7rif Zinc oxide Ta, 7jf N,N-bis-methoxyethylhydroxyamine 761 Triethanolamine solution tL (triethanolamine≠, j parts to 6.2 parts of water)/7. /4Af Tetrahydropyrimidinethione θ, ri-J′o-λ, dimercaptopyrimidine 0, J J゛Q Q uracil toy water /l 3f (4) Development processing and density measurement Photosensitive layer sheet to color temperature 5a00 Light wedge exposure was carried out using a photosensitive layer with a light source. This exposed photosensitive layer sheet and the above image receiving sheet are stacked and the above processing liquid is applied between them.
The film was developed to a thickness of smm and subjected to diffusion transfer development, and after 30 minutes, both sheets were peeled off to obtain a positive image.

This was measured using a TCD type self-recording density needle manufactured by Fuji Film Co., Ltd., and the maximum density (Dmax) was determined.

(5) Forced Deterioration Test a) Forced Sample Forced Deterioration Test The undeveloped image receiving element was
After being left under 0'C and dry conditions for 72 hours, it was developed in the same manner as in (4) above.

b) Forced fading test of transferred image The transferred image obtained by developing in the same manner as in (4) above was treated with l, Q 0 (:, 70% old (, and
It was placed under the conditions of 0% I(, H) for 72 hours and fading was evaluated.

(6) Results Tests were conducted using elements A-/ to A-j.

The obtained results are summarized in Table 1.

In this table, all tones of the transferred image are entered in r.

Image-receiving elements A-/, A-2, and A-j using the compounds of the present invention had higher maximum densities immediately after treatment than A-li, which is the image-receiving element of the comparative example, and the highest density in the forced image deterioration test. The decrease in density is equivalent to A-≠, and the decrease in maximum density is also small in the forced deterioration test of samples before processing. Therefore, the use of the compound of the present invention improves image stability and storage stability before processing. It is clear that both are improved.

The above results show that although the comparative example A-44 has an image stabilizing effect compared to A-j which does not contain an image stabilizer, it has poor storage stability before processing. The improvement effect is obvious.

Patent applicant Fuji: JL Film Co., Ltd.

Claims (1)

[Scope of Claims] Silver salt diffusion transfer method image-receiving element characterized by containing a compound represented by the following general formula CI) General formula (1) % Formula %