JPS61186959A - Image formation by diffusion transfer of silver salt - Google Patents

Abstract

PURPOSE:To prevent precipitation of crystals on the surface of an image by incorporating at least 2 kinds of specified silver halide solvents and incorporating a maleic acid copolymer in an image receving element. CONSTITUTION:The compds. to be used as the silver halide solvents are at least 2 kinds of compds. represented by formula (I) and (II) in which R1, R5 are each alkyl; R2, R6 are each H, alkyl, or halogen; R3, R4, R7, R8 are each H or alkyl; and m, n are each an integer of 0-5. The maleic acid copolymer and/or acrylic acid copolymer has, preferably, an average mol.wt. of 10.000-1,000,000, and it is used, preferably, in an amt. of 0.1-20g/m<2> of the image receiving layer, and in a whole copolymer/binder ratio of 1/9-2/3.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an image forming method by silver salt diffusion transfer and a film unit used therein.

(Prior Art) Image forming methods by diffusion transfer using silver salts such as silver halides are well known. To explain this method specifically, for example, an imagewise 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 treated with the developer. On the other hand, unexposed silver halide grains are converted into a transferable silver complex salt using a silver halide solvent, and this silver complex salt is diffused by inhibition into a silver precipitant-containing layer (image-receiving layer) overlaid with the emulsion layer. - It consists of transferring and then reducing the silver complex salt with a developer with the help 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 layer containing a silver precipitant on a support, an image-receiving element, a developer, a halogen A film unit is used which combines a processing element consisting of a breakable container containing an active alkaline aqueous solution containing a silveride solvent and a thickener. First, the emulsion layer of the light-sensitive element is imagewise exposed, and then the light-sensitive 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 developed. The image-receiving element is passed between a pair of rollers as shown in FIG.

Various proposals have been made to ensure that good images formed in this manner can withstand long-term storage. Especially Tokko Akira! ? -μriIr
The invention disclosed in No. eI discloses a method of using a borate compound in a processing composition as a method for suppressing the formation of undesirable crystalline substances and salting-out compositions during storage of additive color images. ing.

(Problem to be Solved by the Invention) However, it has been found that when this borate is used in large quantities, it may be difficult to uniformly spread the treatment element.

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 method for providing images that are stable for long-term storage.

(Means for Solving the Problems) Therefore, the present inventors have found that when a maleic acid copolymer and/or an acrylic acid copolymer is present in the image-receiving layer, there is little dependence on the amount added and the image quality is improved. We have thoroughly studied methods to extremely strongly suppress the generation of crystals or salting-out compounds during storage.
As a result, the above effects can be achieved by using dihydroxypyrimidine containing at least two or more types of thioether groups, and the generation of crystals can be prevented by using a maleic acid copolymer and/or an acrylic acid copolymer in the image-receiving layer. We have found that this is greatly promoted when

That is, in one aspect of the present invention, an imagewise exposed and subsequently light-sensitive silver halide emulsion layer is developed in the presence of a developer, a silver halide solvent, and an alkali to remove unexposed silver halide in the emulsion layer. Transferring at least a portion of the complex salt to a silver precipitant-containing image-receiving layer 1-
In the image forming method by silver salt diffusion transfer, which comprises forming an image on the image-receiving layer with a silver halide solvent, at least two compounds selected from the following general formula (I) and general formula (II) are used as the silver halide solvent. An image forming method by silver salt diffusion transfer, characterized in that the image receiving element containing seeds and the image receiving layer contains a maleic acid copolymer and/or an acrylic acid copolymer.

(I) (n) In the formula, R and R5H each represent an alkyl group, R and R6 each represent a hydrogen atom, one alkyl group represents a halogen atom, and R3, R4, R7 and R8fl each represent a hydrogen atom or It represents an alkyl group, and m and n each represent an integer from 0 to j.

The alkyl group represented by R and R5 preferably has l-μ carbon atoms, such as methyl, ethyl, isopropyl, orbutyl.

The alkyl group can also be a thioether substituent (e.g. CH35-
), hydroxyl group, carboxy group, amino group, alkoxy group (preferably p/~3 carbon atoms), etc. may be substituted.

The alkyl group represented by R and R6 preferably has a carbon number of I~! The alkyl groups represented by R3, R4, R7 and R8 preferably have 1 to 3 carbon atoms.

Preferably, m and n are each l or λ.

Specific examples of preferred compounds of general formula (I) or (II) are shown below.

i-/ l-2 [-J 1-, t [-/ [-J The compound represented by the above general formula (I) or (If) is
Special public Akira! ≠−λ/ J j O1 US Patent≠.

l Kobu, Hirojri, same≠, 2//, J-1? , same≠.

Those described in λ//, Itco, and those not described can be easily synthesized by referring to the above-mentioned Tokko Shoyu.

Specific examples of preferred copolymers of maleic acid or acrylic acid are shown below.

(a) Styrene-maleic anhydride copolymer (b) x
f-ren-maleic anhydride copolymer (C) Methyl vinyl ether-maleic anhydride copolymer (d) Acrylic acid-alkyl acrylate copolymer (e) Acrylic acid-alkyl methacrylate copolymer (f)) Taacrylic acid-alkyl Acrylate copolymer (2)) Methacrylic acid-alkyl methacrylate copolymer (h) Styrene-maleic acid copolymer (i) Ethylene-maleic & copolymer
-/λt, 22μ, Tokukai Akira! ta 202μ63, Tokko Sho≠μ-/yo7I! , U.S. Pat. No. 3,31,2. tλl etc.

The present invention will be explained in more detail below.

In the imaging method and film unit of the present invention, a developer may be present in the photosensitive element or processing element. Developers such as hydroquinone, tert-butylhydroquinone, p-aminophenol, etc., have a hydroxy group and/or an amino group in the ortho position. :M benzene or naphthalene-based organic compounds are used.

Furthermore, US Patent 3. t/J-, μμO, and U.S. Pat. No. 3,730,7/l,
The α,β-enediols described in the above are preferably used. Further, U.S. Patent J, 21r? ,/j
Hydroxylamine developers such as those described in No. J and No. 3,223,03μ are particularly preferably used.

Further, as a developer, the l-aryl-3-pyrazolidinone compound described in the invention in Japanese Patent Publication No. 1 Jr. may be used in combination with the above developer.

The silver halide solvent of the present invention is preferably present in the processing element.

The alkaline agent that makes the pH of the treatment composition alkaline (preferably pH 1.2 to lμ) is preferably an alkali metal hydroxide, particularly sodium hydroxide, potassium hydroxide, and/or lithium hydroxide. .

Total amount of dihydroxypyrimidine compound used: 1410
09 to 3077 per treatment solution is preferred, with a minimum amount of a single compound of 10017 O0Q per treatment solution! I is preferred.

The usage ratio of these compounds depends on the grain size, grain shape, halogen composition, and silver amount of the silver halide used, as well as the type and amount of the developer used, and the halogen content of the dihydroxypyrimidine compound used. Although it cannot be determined unambiguously depending on silver oxide solubility, in industrial practice, the minimum ratio of a single dihydroxypyrimidine compound used is approximately / / of the total dihydroxypyrimidine compound.
100 (by molar ratio) is preferred, and about 1/10 (by molar ratio) is more preferred.

The amount of developer used should be 10x10-3 to
0, J mol, &'1L (ldFX/θ ~0・μ
mol, more preferably /x10 -0°3 mol.

When the processing liquid of the present invention is applied by distributing it as a thin layer between a superimposed photosensitive element and an image receiving element, the processing liquid does not contain a polymeric film former, a thickening agent or a thickening agent. Preferably. Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful for hazing for this purpose and are included in the processing solution at concentrations effective to provide the appropriate viscosity according to known principles of diffusion transfer photography. The processing solution may further contain other auxiliary agents known in the silver salt diffusion transfer process, such as antifoggants, toning agents, stabilizers, and the like. In particular, the inclusion of oxyethylamino compounds such as triethanolamine is described in US Pat. No. 3,419,11! It is useful for increasing the shelf life of processing solutions.

The processing liquid as described above is preferably stored in a breakable container to serve as a processing element. Any breakable container and material known in the art may be used; for example, U.S. Patent No. 3.0 Taro, μ
ri No. 1, ri No. 3. Oj4.44 Octopus, same! , /73,1
No. 10, 3゜7rO, No. 07, 3.133.31
No. 1, same μ, 303.7 and No. 0, same μ, 303.7J-
It is described in detail in issue 1 etc.

The maleic acid copolymer and/or acrylic acid copolymer used in the image receiving element is a binder, i.e., cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl It is preferably contained in polyvinyl esters such as propionate and polyvinyl chloroacetate.

Also, the maleic acid copolymer and/or acrylic acid copolymer used has an average molecular weight of 10°000, /
000.000 is preferable, and the usage amount is lff
! Per o, tp ~ 209 is preferred. Furthermore/,
/Oi is most preferred.

In the present invention, the total copolymer/binder ratio of the maleic acid copolymer and/or acrylic acid copolymer used in the image receiving element is preferably 1/2 to 3/2, and 377 to 3/1.
is even more preferable.

Although the maleic acid copolymer and/or the acrylic acid copolymer are preferably contained in the neutralization layer, a portion of the entire copolymer may be contained in the neutralization timing layer.

It is effective as a neutralizing agent for alkaline agents that permeate the maleic acid copolymer and acrylic acid copolymer used in the present invention.

It is also preferred to provide a layer (timing layer) of a suitable cellulose ester, such as cellulose diacetate, between the intermediate layer and the acid copolymer layer.

Furthermore, the image-receiving element of the present invention includes a support carrying an image-receiving layer containing a silver precipitant, such as baryta paper, cellulose triacetate or polyesters. Such image receiving elements can be prepared by coating an optionally subbed support with a coating solution of a suitable cellulose ester, such as cellulose diacetate, preferably dispersed with a silver precipitating agent. The resulting layer of cellulose ester is subjected to alkaline hydrolysis to convert at least a depthwise portion of the cellulose ester to cellulose. In particularly useful embodiments, silver precipitating agents and/or
The unhydrolyzed portions of the underlying cellulose ester layer containing cellulose esters, e.g. cellulose diacetate, which have not undergone hydrolysis, improve the tone, stability or other photographic properties of the silver transfer image. Contains one or more mercapto compounds that can be used to Such a mercapto compound is utilized during imbibition by diffusing from the 11.7'h position where it is first placed. This type of receiver element is described in U.S. Patent No. 3,607.
．． It is written in Ko6ri issue.

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 noradium. Other useful silver precipitating agents are sulfides and selenides of heavy metals, especially mercury, copper, aluminium, zinc, cadmium, cobalt, nickel, silver, lead, antimony, bismuth, cerium and magnesium, and sulfides of lead, zinc. , antimony and nickel selenide. Regarding the function of materials such as silver precipitants in the silver salt diffusion transfer method, see, for example, U.S. Pat.
μ, No. 447.

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

It is also preferable to provide a peeling layer on the surface of the image-receiving layer in order to prevent the treatment liquid from adhering to the surface of the image-receiving layer during peeling after the treatment liquid is developed. Preferred release layers include gum arabic, hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, polyacrylamide, sodium alginate, and US Pat.
Mention may be made of those described in No. 72,02μ, No. 3,120, Tatata and British Patent No. 360,663.

In particular embodiments of the invention, image-receiving layers can be incorporated into the photosensitive elements described below. For example, on a polyethylene terephthalate sheet, an image-receiving layer containing a silver precipitant, a light-reflecting layer containing a white pigment such as titanium dioxide, a phosphorescent layer containing a light-absorbing substance such as carbon black, 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 photosensitive silver halide emulsion layer after the diffusion transfer process, so that the image formed on the image-receiving layer can be observed through the polyethylene terephthalate sheet. can do.

Further, in the present invention, a photosensitive element obtained by coating a photosensitive silver halide emulsion on a support is preferred.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the hanosilver halide in the photosensitive silver halide emulsion used in the present invention.

Preferred silver halide is silver iodobromide or silver iodochlorobromide containing 10 mol % or less of silver iodide. Particularly preferable is 3
Silver iodobromide containing from mol % to 10 mol % silver iodide.

The average grain size of the silver halide grains in the light-sensitive emulsion (grain diameter in the case of spherical or approximately spherical grains, grain size in the case of cubic grains, expressed as an average based on the projected area) is not particularly limited. is preferably 3μ or less, 1
．． 5 μ or less is preferable, and particularly preferable is O8r~1
．． λμ.

The particle size distribution may be narrow or wide.

The silver halide grains in the light-sensitive emulsion may have equiaxed crystal forms such as cubic or octahedral, or may have irregular crystal forms such as spherical or plate-like. It may also have a composite crystalline form. It may also consist of a mixture of particles of different crystalline forms.

The silver halide grains may have an inner layer and a surface layer composed of different phases, or may be emitted from a uniform phase. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. Preferably, the latent image is formed primarily on the surface of the particles.

The thickness of the photosensitive emulsion layer is 0°5~g, Oμ, especially 0,
/J-1゜Oμ, and 1 liter of coating of halogenated steel particles
Jt O, / ~ J Ii7'm 2, preferably O8
2~1,s! 9/,,2.

The light-sensitive emulsion is prepared by a method commonly used for silver halide photographic emulsions, chemical sensitization and spectral sensitization are performed as necessary, and the emulsion contains antifoggants, stabilizers, hardeners, coating aids, It may contain an antistatic agent and the like. Also, a vehicle such as gelatin is used in the emulsion.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Any of a wide variety of known light sources can be used, such as fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. Exposure time varies from 17iooo seconds normally used in cameras to 1
As well as exposure times shorter than 171,000 seconds, e.g. using xenon flash lamps or cathode ray tubes.
'~l/lO An exposure of 6 seconds or a longer exposure of 1 second can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. A laser source can also be used for exposure.

Alternatively, exposure may be performed using a source excited by electron beams, X1@, r-rays, α-rays, etc. and emitted from a constant phosphor.

Regarding the arrangement and joining method of each element to combine the photosensitive element, image receiving element, and processing element as described above to form a film unit, for example, Nebret (
Handbook of Photography (HAND BOOK O)
F PH0TOGRA PHYAND REPROGRA
PHY), 7th edition, pages 2g2-2♂, and a particularly preferred embodiment is described in U.S. Pat.
There are detailed explanations in the issue, so you can refer to them.

(Effects of the Invention) The dihydroxypyrimidine compound represented by formula (I) or (II) used in the present invention is disclosed in US Pat.

Tatata and U.S. Pat. There is a description that it can be used together with a silver halide solvent.

On the other hand, when an image print is stored for a long period of time, crystals are generated on the surface of the print. It has been found that the generation is promoted by the maleic acid copolymer and acrylic acid copolymer constituting the image print, and that crystals are generated when the dihydroxypyrimidine compound is used alone.

However, it has been found that by using two or more specific compounds represented by formula (I) or (ff) in a specific ratio, the formation of the above-mentioned crystals does not occur substantially. Served.

In this respect, it is clear that the present invention is in no way analogous to the above-mentioned US Pat.

Thus, according to the present invention, when using an image receiving sheet containing a maleic acid copolymer and/or an acrylic acid copolymer,
By using two or more types of dihydroxypyrimidine compounds in combination, long-term preservation of images and, in particular, prevention of crystallization on the image surface can be achieved.

(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 Silver halide 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 (with a lower iodine content).

The average diameter of the silver halide grains contained in this emulsion was O, Tamikron.

This emulsion/kp contained Bo and tr moles of silver halide. This emulsion was collected in pots in batches of / and p, dissolved in a constant temperature pass of zooc, and ortho-sensitizing dye 3-(j-chloro4-2-[λ-ethyl-3-(3- Ethyl-2-penzothiazolinylidene)pronyl-3-penzoxazolio)prono-sulfonate, panchromatic sensitizing dye Q-(2-((J-ethylbenzotheazoline-λ-yritene)-comethyl-7 −
[probenyl]-3-benzothiazolio)butane-sulfonate and μm hydroxy-ot-methyl-l, 3゜3a,
/wt% aqueous solution of 7-chitrazaindene, 10 ml of a 7 wt% aqueous solution of 6-cyclotriazine sodium salt, 10 ml of a 1 wt% aqueous solution of sodium dodecylbenzenesulfonate, lipoic acid,
A methanol solution of 1% by weight was added, and the mixture was mixed and stirred under JooC. This loaded emulsion was applied to a polyethylene terephthalate film base containing titanium dioxide that had been primed to a dry film thickness of 3 microns, and dried to obtain a sample. At the same time, polymethyl methacrylate latex (average size 3, !μ) was added to the gelatin aqueous solution and coated to a dry film thickness of 7 microns. The amount of nine silver coated was 0.67 m2.

On an image-receiving sheet of polyethylene laminated paper, lrg of cellulose acetate (acetate %) and 12 fl of styrene-maleic anhydride copolymer/21/ or acrylic acid-alkyl acrylate copolymer shown in the following table were applied. acetone 27
Dissolved in θ- and 30 vil of methanol and 7? : Apply the solution to a thickness of 5 ml/m 2 and dry it, then apply it on top of this at a thickness of 0,019 ml/m 3. t-Schiff x=, 1b −/
, 4t-shi) I Roux 1y Budou jH, AH-2゜3
a,! , ta-tetraza was coated with a 10% cellulose acetate acetone solution of ntalene so that the dry film thickness was 1017 m2. Furthermore, on top of this, dimethylol urea (5%) aqueous solution and acetic acid (
I0%) were added and mixed at concentrations of 5%, 1, and 2%, respectively, and 2! The coating thickness was 7 m2. Furthermore, a solution of 3% cellulose acetate in acetone/methanol (Li/l) in which palladium sulfide was finely dispersed was applied. This coating solution contained phenyl-j-mercaptoimidazole in a coating amount of 2.times.10 mol/m.sup.2. The dry film thickness was O0tμm. Add the following alkaline solution to this coating material / r ml /
An image-receiving sheet was prepared by coating the film at a ratio of m2, washing with water and drying. The above Noradium sulfide dispersion C, 5.3% acetone/methanol (li//) of cellulose acetate
A methanol solution of 7X/(7-3 moles of sulfurized sodium chloride) of sodium palladium chloride (7-3 moles) was added to the mixed solution and stirred thoroughly.

Treatment liquid potassium hydroxide<rs%) Cotop titanium dioxide 3g hydroxyethyl cellulose 7077 zinc oxide
/QflN, N-bismethoxyethylhydroxylamine taptriethanolamine 7I tetrahydropyrimidinethione o, lAg2, μm dimercaptopyrimidine 0,3jpx-n propylthiouracil
Add the following compound to the above processing solution and further add water to make the total amount 2. Next, spread the processing solution between the photosensitive sheet and the image-receiving sheet, and wait for 3 minutes. Peeling friend.

The amount of these additives was determined so that the image sensitivity, gradation, maximum density, minimum density, and charging time were the same as in Example 1 of Table 1. The resulting image was left at room temperature for one week, and the surface condition of the image at that time was observed.

As shown in Table 1, when a vinegar copolymer layer is present, crystals are generated on the print surface, but by using a combination of multiple dihydroxypyrimidine compounds of the present invention, even if an acid copolymer is present, crystals are formed on the print surface. It turns out that it does not occur.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Date: March 1985 /・−(゛2χ′)・−1t) 1. Display of the incident.

Patent application 2 filed on February 13, 1985, Title of invention: Image forming method by silver salt diffusion transfer 3, Relationship to the case of the person making the amendment Person of the patent applicant Location: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photographic Film Co., Ltd. 4. The subject of the amendment The "Claims" column and the "Detailed Description of the Invention" column of the specification and the contents of the amendment Correct as expected.

The description in the "Detailed Description of the Invention" section of the specification is amended as follows.

/) Page 6, line j ” and correct it.

λ) 1st page l second row K after “Rum” ", gold, platinum, palladium" Insert.

J) First page, line 7 "Preferable, /, 1μ" "Preferably, furthermore/, jμ" and correct it.

Claims Imagewise exposed nine light-sensitive silver halide emulsion layers [IJ,
developed in the presence of a silver halide solvent and an alkali;
A silver salt comprising converting at least a portion of the unexposed silver halide in the emulsion layer into a transferable silver complex salt, and transferring at least a portion of the complex salt to an image-receiving layer containing a silver precipitant to form an image on the image-receiving layer. In the image forming method by diffusion transfer, the following general formula (I) and general formula (I) are used as the silver halide solvent.
Silver salt diffusion characterized by containing at least two compounds selected from the compounds represented by [), and containing a maleic acid copolymer and/or an acrylic acid copolymer in the wound element including the image-receiving layer. Image forming method by transfer.

In the formula, R1 and R5 each represent an alkyl group, and R2
and R6 each represent a hydrogen atom, an alkyl group or a halogen atom, R3, R4, R7 and R8 each represent a hydrogen atom or an alkyl group, and m and n each represent an integer of 0-2.

Claims (1)

[Claims] An imagewise exposed photosensitive silver halide emulsion layer is developed in the presence of a developer, a silver halide solvent and an alkali to transfer at least a portion of the unexposed silver halide of the emulsion layer. In the image forming method by silver salt diffusion transfer, which includes transferring at least a part of the complex salt to an image receiving layer containing a silver precipitant to form an image on the image receiving layer, the silver halide solvent is as follows: General formula (I) and general formula (II
), and the image receiving element including the image receiving layer contains a maleic acid copolymer and/or an acrylic acid copolymer. image forming method. (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II)▲
There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_5 each represent an alkyl group,
R_2 and R_6 each represent a hydrogen atom, an alkyl group or a halogen atom, and R_3, R_4, R_7 and R
Each of _8 represents a hydrogen atom or an alkyl group, and m and n each represent an integer of 0 to 5.