JPS6143742A - Processing composition for silver salt diffusion transfer process - Google Patents

Abstract

PURPOSE:To enhance stability during long period storage by incorporating as a developer a compsn. contg. a compd. which deprives a compd. represented by a specified formula of 50-98% dicarboxylic acid with respect to hydroxylamine. CONSTITUTION:An imagewise exposed photosensitive silver halide emulsion layer is developed in the presence of a silver halide solvent, alkali, and a developer of a compsn. contg. a compd. which diprives a compd. represented by formula (R1 is alkyl or alkoxyalkyl, R2 is H, alkyl, or alkoxyalkyl, and n is an integer of 0-3) of 50-98% dicarboxylic acid with respect to hydroxylamine. At least a part of the unexposed silver halide of the emulsion layer is converted into a transferable silver salt, and a part of this salt is transferred to an image receiving layer contg. a silver precipitating agent, thus permitting an image to be formed on the image receiving layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a processing composition for silver salt diffusion transfer and an image forming method by silver salt diffusion transfer.

(Prior Art) Image forming methods by diffusion transfer using silver salts such as silver halides are well known. Specifically, the Sugi method is such that, for example, an image-exposed photosensitive silver halide emulsion layer is treated with an alkaline aqueous solution containing a developer and a silver halide solvent, and the exposed silver halide grains are converted into silver by the developer. On the other hand, the unexposed silver halide grains are converted into a transferable silver complex salt using a silver halide solvent, and this silver complex salt is transferred by imbivision to a silver precipitant-containing layer (image-receiving layer) superimposed on the emulsion layer. The process consists of diffusing and transferring the silver complex salt, and then reducing the silver complex salt with a developer with the aid of a silver precipitant to obtain a silver image.

When carrying out this method, for example, a light-sensitive element having a light-sensitive silver halide emulsion layer on a support, an image-receiving element having an image-receiving layer containing a silver precipitant on a support, a developer, a halogenated A film unit is used which combines processing elements such as a breakable container containing an active alkaline aqueous solution containing a silver solvent and a thickener. First, the emulsion layer of the photosensitive element is imagewise exposed, and then the photosensitive element and the image receiving element are overlapped so that the emulsion layer and the image receiving layer of the image receiving element face each other, while the processing element is destroyed and a viscous alkaline aqueous solution is The image-receiving element is passed between a pair of rollers so as to be developed, and after being left for a predetermined period of time, the image-receiving element is peeled off from the photosensitive element, thereby obtaining a print in which a desired image is formed on the image-receiving layer.

There are three US patents for the developer used when forming such images! Preferred are the hydroxylamine compounds described in No. r7/2r and No. 32-303,
Since these compounds themselves deteriorate rapidly during storage, their storage methods (temperature, packaging form, etc.) require strict control, and improvements in this respect have been desired.

The present inventors searched for a developer that is stable for long-term storage and has high activity, and found that it is effective to use a hydroxylamine dicarboxylate salt as shown in the general formula. When an image print made using salt was left for several months, white crystals began to precipitate on the surface of the print. As a result of investigating the cause, it was found that dicarboxylic acid crystals were precipitated.

(Object of the Invention) An object of the present invention is to provide a novel image forming method using silver salt diffusion transfer.

Another object of the present invention is to provide a developer for silver salt diffusion transfer method that is stable during long-term storage.

Another object of the present invention is to provide a silver salt diffusion conversion processing composition that does not cause crystals to appear on the image surface after image formation.

(Structure of the Invention) As a result of intensive studies on a highly active developer that can withstand long-term storage and a method of obtaining prints that can withstand long-term storage, the above-mentioned developer contains a compound represented by the following general formula ([)] From about SO to about 30% for hydroxylamine from the composition
This was achieved by a processing composition for a silver salt diffusion transfer method, which is characterized in that it contains a composition obtained by removing dicarboxylic acid of =S as a developer.

CI) I(,-N-8,2・f(OOC(CH2
) nCOHOH In the formula, R is an alkyl group or an alkoxyalkyl group,
R12 represents hydrogen, an alkyl group, or an alkoxyalkyl group, and n represents an integer of O to 3.

The composition containing the compound represented by the above general formula (1) is preferably an aqueous solution containing the compound, but solvents other than water, such as methanol, ethanol, or dimethylformamide, may also be used. The above aqueous solution may contain t-50% or less, preferably 10% (f) or less of a solvent other than the above-mentioned water.

In general, hydroxylamine dicarboxylic acid salts can be synthesized by dissolving hydroxylamine and dicarboxylic acid in a solvent and separating the precipitated hydroxylamine/dicarboxylic acid (preferably under cooling). The solubility of hydroxylamine and dicarboxylic acid is high in the solvent used, but it is desirable that the solubility of hydroxylamine/dicarboxylic acid is small, and the amount of dicarboxylic acid used is usually 7 to 5 times the molar equivalent of hydroxylamine. However, it is preferably used in an amount of 2 to 3 times the molar equivalent. In addition, examples of acids that generally form salts with hydroxylamine include hydrochloric acid, sulfuric acid, phosphoric acid, dicarboxylic acid, and di-)lue/sulfonic acid, but dicarboxylic acids tend to crystallize with respect to hydroxylamine. From a synthetic standpoint, dicarboxylic acids are preferred.

Typical methods for removing about 50 moles of dicarboxylic acid from compositions containing hydroxylamine dicarboxylate, particularly from an aqueous solution of hydroxylamine, are as follows: (1) Method of precipitating as an alkali dicarboxylic acid by adding an alkali agent. , alkali metal hydroxides, carbonates,
Phosphates and borates are preferred, and the alkali metals are preferably sodium, potassium, calcium, and barium, and among them, sodium carbonate is most preferred.

The amount of dicarboxylic acid removed is determined by the amount of alkaline agent added.

(2) Ion-exchangeable exchange group by anion-exchange resin is O
Typical examples include H group and α group, but OH group is most preferred.

Both strongly basic and weakly basic anion exchange resins are suitable, but strongly basic anion exchange resins are most suitable.

The amount of dicarboxylic acid removed is determined by the type of anion exchange resin, its amount, and the contact time of the resin with the aqueous hydroxylamine solution.

The above object is achieved by the following aspects.

The imagewise exposed photosensitive silver halide emulsion layer is developed in the presence of a developer, a silver halide solvent and an alkali to convert at least a portion of the unexposed silver halide in the emulsion layer into a transferable silver complex salt. In an image forming method by diffusion transfer, which includes transferring at least a portion of the complex salt to an image receiving layer containing a silver precipitant-containing layer to form an image on the image receiving layer, a compound represented by the following general formula CI) is used. 1. A method for forming an image by silver salt diffusion transfer, characterized in that a composition obtained by removing about 50 to about 50% dicarboxylic acid relative to hydroxylamine from a composition containing the hydroxylamine is used as a total developer.

In the formula, R1 is an alkyl group or an alkogyalkyl group,
R2 is hydrogen, an alkyl group, or an alkoxyalkyl group,
n represents all integers from O to 3.

Preferably, an aqueous solution containing a compound represented by the following general formula (i) is used, so that the amount of hydroxylamine is approximately 1. 0 to about 2
This is an image forming method by silver salt diffusion transfer, which is characterized in that an aqueous solution obtained by removing dicarboxylic acid 1- is used as a developer.

(1) u, -N-R2-HOOC(CH2)nCO
In the OH formula, R represents an alkyl group or an alkoxyalkyl group, R2 represents hydrogen, an alkyl group, or an alkoxyalkyl group, and n represents an integer of O to 3.

In the image forming method described above, it is preferable to treat the image-exposed photosensitive silver halide emulsion layer with an alkaline processing composition containing a developer and a silver halide solvent, which will be described in detail below.

Hydroxylamine as a developer is present in the processing composition/0
0 per 0f. It is preferable to contain /-/jf, and 1
2~j? is most preferred.

Further, as a developer, l-aryl-3-pyrazoline non-converted @ compound described in the invention of Japanese Patent Publication No. 1 Jj IrO may be used in combination.

Silver halide solvents may be present in the processing element, the light-sensitive element and/or the image-receiving element. Among these, it is preferable that the processing element is a drum. U.S. Patent No. 1j7ko7hiro, U.S. Patent No. 211727j
The cyclic compounds described in No. and No. 2117274 are suitable, and among p1, uracil, urazol, 6-methyluracil, etc. are preferred examples.

Further preference is given to alkali metal thiosulfates, especially the sodium or potassium salts, and also as described in US Pat. No. 32Jt? Octopus No. 327, Otsu≠7 No. 7, vJ No. 00ri No. 767, No. 1A032j31, Iif[4'oatstr No.
Same No. 4LOu7Y14A4j, Same No.≠O≠72jj,
No. 107/74 and the disulfonylmethane compound of JP-A No. 7-JJO and the U.S. Patent No. 7-JJO! No. 2,
The same number Hiroiroko λ, the same number ≠ ko //! ! No. 2 and the same@g, sulfur uracil compounds of No. 211jtJ and US Patent No. guco! /617, No. 1A2t7.2j Hiro, and Aminothioether No. 2t72jt. These can be used alone or in combination, and when a bipolar or more cyclic imide compound is used in combination, there is an advantage that white crystals will not precipitate on the surface of the print even if the print is stored for a long period of time.

The amount of silver halide solvent added is 0 per 1002 of the processing composition.
．． It is preferable to contain /~307, O1!2~1
0y is most preferred.

Examples of hydroxylamine dicarbo/acid salts are shown below.

When the processing composition of the present invention is applied by distributing it as a thin layer between a superimposed photosensitive element and an image receiving element, it is particularly advantageous to distribute the processing compositions so that these elements are in a symmetrical relationship. If so, the treatment composition preferably contains a polymeric film-forming agent, a thickening agent, or a thickening agent. Droxyethylcellulose and sodium dimethylcellulose are particularly useful for this purpose and are included in the processing composition in concentrations effective to provide a suitable viscosity according to the well-known principles of the diffusion transfer process. let The processing composition may further contain other auxiliaries known in the silver salt diffusion transfer process, such as antifoggants, toning agents, etc.
ng agents), stabilizers, and the like. In particular, the inclusion of oxyethylamino compounds, such as triethanolamine/
iyirz, is useful for increasing the shelf life of treatment compositions.

The treatment composition of the present invention is preferably packaged in a breakable container to form a treatment element. Any breakable container and material known in the art can be used, and these are described, for example, in U.S. Pat.
4, ≠ri No. 7, same No. 3゜osA, uya No. 3, same No. 3.
/73,110, @3,710,207, same #3
, No. 133゜3ri, No.≠, 303.7. jrO,
Same@gu.

It is described in detail in JOJ, issue 71/etc.

On the other hand, the support material used in the present invention includes a support carrying an image-receiving layer of an alkali-permeable polymer (particularly regenerated cellulose) containing a silver precipitating agent, such as baryta paper, cellulose triacetate, or polyesters. Such receiver elements can be prepared by coating an optionally primed support with a coating solution of a suitable cellulose ester, such as cellulose diacetate, in which a silver precipitant is dispersed. The cellulose ester layer is subjected to alkaline hydrolysis to convert at least a portion of the cellulose ester in the direction of deep transformation into cellulose. In a particularly useful embodiment, the portion of the cellulose ester layer that did not undergo hydrolysis, containing a silver precipitant and/or an underlying cellulose ester that did not undergo hydrolysis, such as cellulose diacetate, Contains seven or more mercapto compounds suitable for improving image tone, stability or other photographic properties.

This stronger mercapto compound is utilized during imbibition by diffusing from the position where it was initially placed. This type of receiver element is described in US Pat. No. 3,607.24P.

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 F'i sulfides and selenides of heavy metals, especially mercury, copper, aluminum, zinc,
Mention may be made of sulfides of cadmium, cobalt, nickel, L lead, antimony, bismuth, cerium and magnesium, and selenides of lead, zinc, antimony/and nickel. Regarding the function of materials such as silver precipitants in the silver salt diffusion transfer method, see, for example, U.S. Patent No.
77≠, described in No. t67.

Further, it is preferable to provide one layer of neutralizing acidic polymer between the image-receiving layer and the support. Preferred acidic polymers include copolymers of unsaturated carboxylic acids such as acrylic acid, maleic acid, methacrylic acid, itaconic acid, crotonic acid;
Includes acidic cellulose derivatives. Specific examples include butyl acrylate/acrylic acid copolymer, cellulose acetate hydrogen phthalate, ethyl methacrylate/methacrylic acid copolymer, and methyl methacrylate/methacrylic acid copolymer. Other useful polymers include sulfonic acid groups such as TRC polystyrene sulfo/acid and acetalized products of benzaldehyde sulfo 7e and polyvinyl alcohol.

Furthermore, it is preferable to provide an intermediate layer between the image-receiving layer and the layer containing a toning agent and a stabilizer. Preferred materials for the intermediate layer include gum arabic, polyvinyl alcohol, and polyacrylamide.

In addition, on the surface of the image-receiving layer, in order to prevent the processing composition from adhering to the surface of the image-receiving layer during peeling after spreading the processing composition,
Preferably, a release layer is provided.

In addition to gum arabic, hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, polyacrylamide, and sodium alginate, preferable materials for such a release layer include U.S. Pat. and UK patent @/, JAθ,t
! Examples include those described in No. 3.

In a particular embodiment of the invention, the image-receiving layer can be incorporated into the CPVC of the photosensitive element described below. For example, on a transparent polyethylene prephthalate sheet, in order, an image-receiving layer containing a silver precipitant, a light-reflecting layer containing a white pigment such as titanium dioxide, a light-shielding layer containing a light-absorbing substance such as carbon blank, and a photosensitive layer A preferred example is one provided with a silver halide emulsion layer. In such an embodiment, the light-reflecting layer shields the layer behind the light-sensitive silver halide emulsion layer without peeling it off after the diffusion transfer process.
The image formed on the image-receiving layer can be observed using polyethylene terephthalate-, y-)tm.

Further, the photosensitive element used in the present invention is obtained by coating a photographic emulsion as detailed below on a support.

In the photographic emulsion of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. The preferred silver iodide is silver iodobromide or silver iodochlorobromide containing 10 moles or less of silver iodide. Particularly preferred is silver iodobromide containing from 3 to 70 mole percent silver iodide.

The average grain size of the silver halide grains in the photographic emulsion (expressed as the grain diameter in the case of spherical or approximately spherical grains, and the grain size at the flame contact in the case of cubic grains, expressed as an average based on the projection plane line) is particularly important. No, but preferably 3 μ or less, /,
jμ or less is preferred, and particularly preferred are o, r-/,
, 2μ.

The particle size distribution may be narrow or wide.

The silver halide grains in the photographic emulsion may have equiaxed crystal shapes such as cubic or octahedral, or may have spherical,
It may have an irregular crystal form such as a plate shape, or a composite form of these crystal forms. It may also consist of a mixture of particles of different crystalline forms.

The interior and surface layers of the silver halide grains may be composed of different phases, or may be composed of a uniform phase. It may be a particle in which a latent image is mainly formed on the surface, or it may be a particle in which a latent image is formed in a pattern inside the particle. f
Particles in which the image is mainly formed on the surface are preferable.

The four layers of the photographic emulsion layer are o, j-r, oμ, especially 0°6 to 1
．． 0μ, and the coating amount of silver halide grains is O0l~3
'//m 1 preferably O12~/.

rf/m2.

The photographic emulsion used in the present invention is P, ()lafkide
Cb 1m1e et Physique Pho
tographique (published by Paul Mante1, /y67) G, Ii”.

Photographic Emuls by puffin
ionChemistry (The Focal
Press, /riΔ2), V, L, Zelik
Making and Coa by Man et al.
uing Photographic Emulsion
(Published by The Focal Press, li≦
FJ4 can be mounted using the method described in 2010). 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 halogenide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a substantially uniform grain size can be obtained. 2 formed separately
More than one type of silver halide emulsion may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known tardel water washing method, which involves gelatinization of gelatin, may be used. Inorganic salts (e.g. sodium sulfate), anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid) or gelatin conductors (e.g. aliphatic acylated gelatin,
A sedimentation method (Flocure-7) using aromatic acylated gelatin, etc.) may also be used. The process of removing soluble salts may be omitted.

The silver halide emulsion may be a so-called unripe (Pr1m1 tive) emulsion which is not chemically sensitized, but it is usually chemically sensitized. For chemical sensitization,
Glafkides, Duffin and Ze
lli icman et al. or tfH, Fr.
1eserQ Grundlagen der Pho
tographischenprozesse mit
8i1berhalogenidemulsion
en (AkademischeVerlagge@e
The method described in llschaft, /ritB can be used.

The silver halide emulsion used in the present invention may contain an antifoggant or a stabilizer. Research Disclosure (Re5earc)
h Disclosure) Volume 171゜(/7t4
LJ) Negative 11th l'-Antifoggants
Kumquats are listed in the section of and 5 tabilizers J.

The halogenated emulsion may contain a developing agent. Research Disclosure (Re5earch) is used as a developing agent.
Disclosure) No. 171. Volume (/7611
3) “Developing agents J” on page 22
Those listed in the section can be used.

Silver halide can be dispersed in colloids that can be hardened by various formal or inorganic hardeners.

As a hardening agent, Research Disclosure (Re5
arch Disclosure) Volume 17J (
/7A4! J) All of the items listed in the HardenersJ section of the @JA page can be used.

Silver halide emulsions may contain coating aids. As a coating aid, Research Disclosure (Re5earc)
h Disclosure ) Volume 176 (/71.4
'J) Use those described in the [coating aids] section on page 26.

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

The silver halide emulsion used in the present invention contains Research Disclosure (Re5earchDisc) as a vehicle.
Losure ) Volume 176 (/744t3) Page 26 "Vehicles and vehicles"
The vehicle described in ``Extenders J'' (Ill. 7J, 72) is used.

The silver halide emulsion is coated on a support together with other photographic X layers if necessary. The application method is Research Disclosure.
Volume i7a L/76443) 27th negative rcoatin
gand drying proceduresJ
The method described in section 1 can be used. '*Support Research Disclosure (L(research)
Disclosure) Volume 17j (/76143) Page 2j [5upports JO section] may be used.

The photographic emulsion used in the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thionidel compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane compounds for the purpose of increasing sensitivity, increasing contrast, or accelerating development. It may also contain derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc. For example, U.S. Lli 1% permit No. ≠00,132, Lli No.
Same 3rd. t/7,210, same No. 3,772. Those described in No. 021, No. J, rot, ooJ, etc. can be used.

The photographic emulsion layer and other hydrophilic colloid layers of the photographic material produced according to the present invention may contain water-soluble dyes as filter dyes or for irradiation prevention and other purposes. Dyes include oxonol dyes, hemioxonol dyes, styryl dyes, mero-7anine dyes, cyanine dyes, and azo dyes. Among them, merocyanine dyes such as oxonol dyes and hemioxonol dyes are useful. Dyes are cationic. Certain layers may be mordanted with polymers such as dialkylaminoalkyl acrylates.

In addition to containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of the photographic material produced according to the present invention, they may also be mordanted with a cationic polymer or the like. For example, UK Patent No. 6rz,≠7j, US Patent No. λ, 471. Jet No. 2, 132. poi No. 112゜736, same No. J, oIILr, a
r'y, No. 3°/l≠, No. 302, No. 31≠≠yo, No. 231, West German Patent Application (OLS) No. 1. R≠, J
jJ issue, Tokukai Sho! O-≠762≠ No. 10-7/, J
Polymers described in No. Jλ and the like can be used.

Exposure to obtain a photographic image may be carried out using a conventional method. Sunarichi, natural light (sunlight), tungsten electric light,
Any of a number of known light sources can be used, such as a fluorescent lamp, water lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, etc.

Exposure times range from 17iooo seconds to 1 second, which is normally used in cameras, as well as exposure times shorter than 171,000 seconds, such as those using xenon flash lamps or cathode ray tubes.
Exposures of 0' to //10' seconds can also be used;
Exposures longer than seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, R-rays, α-rays, or the like.

Regarding the arrangement and combination method of each element for combining the specification elements, image receiving element, and processing element as described above to form a film unit, see, for example, Neb l.
e t t e s , HAND BOOK 0FP
HOTOGRAPf(Y AND REPE(, OGR
, APHY 7th edition, 1st to 5th edition! A particularly preferred embodiment is described in U.S. Patent No. J, 310.
, which are explained in detail in the Tatano issue, so you can refer to them.

〔Effect of the invention〕

Thus, with the structure of the present invention, the retention of the developer over time is greatly improved, and furthermore, there is no precipitation of crystals on the image surface after the developer is processed with gold. You can get sharp images in no time.

(Examples) Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to the same extent by these Examples.

Example 1 Removal of dicarboxylic acid salt The following three methods for removing succinic acid using Compound 7 as hydroxylamine dicarboxylic acid were compared.

Neutralization method using sodium carbonate Compound 7/2 to 9f water 1. (1) Sodium carbonate hydrate 401? water 1. Add an aqueous solution dissolved in jl.

(2) To an aqueous solution in which compound 7/, 9 is dissolved in water 21, (2) an aqueous solution in which sodium carbonate aqueous salt 17Of is dissolved in water/, Ill is added.

To a water bath solution in which Compound 7/21q is dissolved in water and 21, (3) an aqueous solution in which sodium carbonate/water salt 3ioyyz water/≠l is added.

Stir each mixture and filter the precipitate using a 30μ ball filter.

(4) Chloroform/
ik, and the chloroform layer is separated and distilled to obtain NN dimethoxyethylhydroxylamine/pure product.

Method using anion exchange resin (6) Dowex SBR, -P(O
H) Soak in 10 il of 4% ft/N sodium hydroxide for 7 days and nights. The soaked resin is filtered and washed three times with water.

This is called preprocessing. Add 161 parts of water to the pretreated resin, and then add 2 kg of Compound 7 and stir. Filter after 3 minutes.

(6) Organo Amberlight IFLAjr Ak
g was pretreated in the same manner as in (5), and then subjected to the same treatment after the pretreatment, and filtered after 4 minutes.

The results are shown in the table below.

NN dimethoxyethylhydroxylamine and succinic acid were both determined by liquid chromatography.

English Example-2 Storage Stability of Recovered Solutions Fill a brown glass bottle with the collected solutions (1) to (6), cap it, and seal it with Teflon tape to prevent it from coming into contact with air.

The table below shows the number of days required for NN dimethoxyethylhydroxylamine to become 7j% of the pre-storage level when stored under Q0C.

Considering transportation to the place of use and from the viewpoint of industrial implementation, according to this test method, the j-th position (dYj%) is sufficient.

Example 3 Silver dihalide grains were formed by a photosensitive sheet single jet method, physically ripened by a conventional method, desalted, and further chemically ripened to form a silver iodobromide emulsion (iodine-containing TJ).

! Morchi) 1: Obtained. The average diameter of the silver halide grains contained in this emulsion was O.tamicron.

1 dJI kg of corn milk contained 0.41 mol of silver halide. Each emulsion tlh was collected in a pot,
It was dissolved in a constant temperature pass to 'C.

Ortho-sensitizing dye (J-(t-chloro-4-[
coethyl-3-(3-ethyl-cobenzothiazolinylidene) propenyl-3-benzoxacilyl 1st pro/cene-sulfonate), [2-ylidene]-comethyl-l-propenyl]-3-benzothiazolioJ propane-sulfonate) hydroxy-bu-methyl-/, 3.Ja, 7-thitrazaindene 1
Weight aqueous solution 10. /lif% aqueous solution of λ-hydroxy-4!6 rhodichlorotriazine sodium salt 10111, and a 1% by weight aqueous solution of sodium dodecylbenzenesulfonate 10. l, lipoic acid 0, /i amount of timetethanol solution 10. and IAOoC were mixed and stirred. This finished emulsion was coated onto a primed titanium dioxide-containing polyethylene terephthalate film base to a dry film thickness of 3 microns and dried to obtain a sample. At the same time, polymethyl methacrylate latex (average size 3.jμ) was added to the gelatin aqueous solution and coated to a dry film thickness of 1 micron. The amount of silver coated was 0.j9/m2.

Image Receiving Sheet A polyethylene laminate paper having a cellulose triacetate layer of 4 μm was immersed in an alkaline hydrolysis solution containing a silver precipitant for 1 minute to prepare an image receiving sheet for diffusion transfer.

The alkaline hydrolyzate was prepared as follows.

Nickel nitrate was dissolved in 2zt/f/f water, added to 100yil of glycerin, and while stirring vigorously, 72% sodium sulfide dissolved in λml of water was further added to make a silver precipitant dispersion of nickel sulfide. .

10100O water dissolved in sodium hydroxide rot-
Add this dispersion to methyl alcohol (1//) solution
In addition, an alkaline hydrolysis solution containing a silver precipitant was prepared.

Treatment liquid (A) Titanium dioxide 3 hydroxyethyl cellulose 7 ta Zinc monoxide
2.7j2 triethanolamine≠j
Aqueous solution /7. lμ2 tetrahydropyrimidinethione o
, 4Ly, ≠-dimercaptopyrimidy O, 36? A-n
Zorovir thiocracil 117. Jyo7 processing [(A
), add the developer from 1 to 7 above as NN dimethoxytyl hydroxylamine in a ratio of 7:1, and further add potassium hydroxide (Hirochi aqueous solution) as free potassium hydroxide in a volume of 343 ml. In addition, the total amount is 9 to λ
Prepare the treatment solution by adding water so that The processing solution was spread between the photosensitive sheet and the image-receiving sheet and then peeled off after j minutes had elapsed.

All of the obtained developers 1 to 7 exhibited the same sensitivity, gradation, maximum density, and minimum density.

Finally, the resulting prints were left at room temperature for one week and the surface condition of the prints was observed.

Example-4 Image-receiving sheet Cellulose acetate (degree of acetylation: J%)/J'S', styrene-maleic anhydride copolymer 2, total acetone core 0d, and methanol 3
A solution dissolved in 011t@jlAwtt/yn'' was coated and dried.
,≠-dimercasotho3-1,1pH-1, Ja, j
, 0.69r% cellulose acetate acetone solution of Aa-tetrazine/talene was prepared so that the dry film thickness was j9/m2.

Furthermore, polyacrylamide is added on top of this! Add dinotyrolurea (5%) aqueous solution and acetic acid (60%) to the aqueous solution! Yu/, Ko! The mixture was mixed in a drying machine and coated at a coating thickness of 2jxt/m2. Furthermore, a liquid containing palladium sulfide finely dispersed in cellulose acetate acetate/methanol d liquid was applied on top of this.

In this Kofu liquid, 7-phenyl-! - Contains mercaptoimidazole. The dry film thickness was o.r.mu.m. This coated material was coated with the following alkaline solution at a ratio of /r, l/WE2, washed with water and dried to produce an image-receiving sheet. The above palladium sulfide dispersion is made of cellulose acetate.
9.Made by adding 7 x 10 mol of sodium sulfide methanol solution and 7XIO mol of sodium palladium chloride methanol solution to a 3% acetone/metal mixed solution and stirring well.

The image-receiving sheet, the same photosensitive sheet as Example 1, and Example-
Processing solutions (0) to (6) prepared in 3.
When the j-wavelength separation was performed, the treatment solution (0) to
In (6), the same sensitivity, gradation, maximum density, and minimum density were obtained, and the surface condition of the resulting print after storage for one week was slightly better than that of Example 30.
Similar results were obtained.

From the above studies, by carrying out the method of the present invention, an active developer that can be stored for a long period of time can be provided, and the resulting prints can be stored for a long period of time.

Procedural amendment

Claims (1)

[Scope of Claims] A developer includes a composition obtained by removing about 50 to about 98% dicarboxylic acid relative to hydroxylamine from a composition containing a compound represented by the following general formula (I). Treatment composition for silver salt diffusion transfer method (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ In the formula, R_1 is an alkyl group or an alkoxyalkyl group, and R_2 is hydrogen, an alkyl group, or an alkoxyalkyl group. , n represents an integer from 0 to 3.