JPS62106457A - Photographic material for diffusion transferring method - Google Patents

Abstract

PURPOSE:To obtain the titled material having a less tendency for generating the irregularity of an image by forming a supporting body of a coated paper. CONSTITUTION:The irregularity of the image can be improved remarkably by forming at least one of the substrate laminated two sheets of papers, preferably an image receiving sheet of the substrate of the coated paper, without almost increasing a production cost. The usable coated paper means a paper coated the surface or the both surfaces of the base paper with a coating material obtd. by mixing a mineral pigment such as a clay and an adhesive. Said coated paper comprises an art paper (coating amount, about 20g/m<2>), a coated paper (coating amount, about 10g/m<2>) and a light weight coated paper (coating amount, about 5g/m<2>) which are classified according to the coated amount of the coated material. And also a cast coated paper having a strong luster which is produced by coating the surface of the base material with the coating material followed by pressing the coated base material with a dryer finished to a specular surface, while remaining plasticity of the coating material and then by drying it, is comprised in said coated paper.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photographic material, and more particularly to a color diffusion transfer photographic material using a direct reversal silver halide emulsion and a silver salt diffusion transfer photographic material. .

(Prior technology) Direct reversal emulsion, photographic material using all direct reversal emulsions,
Regarding color diffusion transfer photographic materials that combine a nucleating agent and an internal latent image type direct reversal emulsion, '[', H,
James ed. The Theory of the Photographic Process
he Photographic Process) th edition (/F77, Mac i I lanPub
It is well known as listed on d6 in lishing Co., Inc.). Furthermore, it is well known that in color light-sensitive materials, by using a multilayer structure of silver halide emulsion layers, color reproducibility can be improved and color images of excellent image quality can be obtained.

In a multilayer color photographic light-sensitive material that combines a nucleating agent and an internal latent image type direct reversal emulsion, development of the silver halide emulsion layer near the support does not occur sufficiently or is strongly affected by processing conditions. .

In particular, it is recommended to increase the transfer speed of images and to
When the thickness of an alkaline processing composition developed for the purpose of improving Yapness is made thinner, development may not occur uniformly and sufficiently, or if the processing conditions are strongly affected, image unevenness may occur due to uneven transfer and development. .

In particular, such a phenomenon applies to color diffusion transfer processes which include at least one internal latent image type direct reversal emulsion layer in combination with a dye image-providing compound on one support and an image-receiving layer on another support. This is particularly noticeable in photographic materials. Moreover, in this case, when paper is used for at least seven supports, this is particularly noticeable when paper is used for the support of an image-receiving sheet having an image-receiving layer.

On the other hand, an image forming method by diffusion transfer using a silver salt such as silver halide is well known. Specifically, the method includes, for example, treating an imagewise exposed photosensitive silver halide emulsion layer with an alkaline aqueous solution containing a developer and a silver halide solvent, and converting the exposed silver halide grains into silver by the developer. On the other hand, the unexposed silver halide grains are made into a transferable silver complex salt using a silver halide solvent, and this silver complex salt is
It consists of diffusing and transferring by imbibition to a silver precipitant-containing layer (image-receiving layer) superimposed on the emulsion layer, and then reducing the silver complex salt with a developer with the help of the silver precipitant to obtain a silver image.

When carrying out this method, in 1-, for example, a photosensitive sheet having a light-sensitive silver halide emulsion layer on a support, an image-receiving sheet having an image-receiving layer containing a precipitating agent on a support, and a developer. A film unit is used which combines a processing element consisting of a breakable container containing active alkaline earth gold containing a silver halide solvent and a thickener. First, the emulsion layer of the photosensitive sheet is subjected to image exposure 1. After that, the photosensitive sheet and the image receiving sheet are overlapped so that the emulsion layer and the image receiving layer of the image receiving sheet face each other, while the processing element is destroyed and a viscous alkaline aqueous solution is applied. The image-receiving sheet 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 sheet is peeled from the photosensitive sheet, thereby obtaining a print in which a desired one-sided image is formed on the image-receiving layer.

In this way, in the Chikara-Ginhana diffusion transfer method, it is possible to increase the transfer speed of the silver image and improve the sharpness of the silver image.
Alternatively, when the thickness of the alkaline processing composition developed for the purpose of improving the storage stability of the image is reduced, development may not occur uniformly and sufficiently, and may be strongly influenced by the processing conditions, resulting in uneven transfer and uneven development. This will cause image unevenness and failure.

This case is also remarkable when paper is used as at least one support, especially the support of an image-receiving sheet having an image-receiving layer.

(Problems to be Solved by the Invention) Such image unevenness varies depending on the thickness of the support of the photosensitive sheet and/or image-receiving sheet used, and the thinner the support is used, the more conspicuous it occurs.

Furthermore, even when the alkali processing composition has a sufficient spread thickness and development is sufficiently performed, image unevenness failures may also occur due to coating unevenness in the coating L- of the photosensitive sheet and/or image-receiving sheet. In this case as well, especially when a paper support is used, uneven coating or drying tends to occur depending on the unevenness of the paper. Furthermore, in both the color diffusion transfer and @salt diffusion transfer photographic materials mentioned above,
Particularly when paper is used as the support for the image-receiving sheet, uneven coating and drying due to organic solvent coating and/or high-temperature coating (Hiro 0°C to /DOj-0C), as well as acceleration of coating drying unevenness due to thermal deformation of the support. Therefore, image unevenness may become a problem.

Therefore, an object of the present invention is to provide a diffusion transfer photographic material in which image unevenness does not occur.

(Means for solving the problem) The present inventors conducted various studies to achieve the above object,
A photosensitive sheet having a light-sensitive silver rokenide emulsion layer of at least 1/l on a support, an image receiving sheet having at least an m image receiving layer on another support, and between these λ sheets. In a diffusion transfer copying material containing an alkaline processing composition to be developed, at least one of the supports used in the co-sheet, preferably the image-receiving sheet support, can be made of coachite paper, without substantially increasing costs. , Can the above-mentioned image unevenness be improved to a great extent? I found it.

The coachite paper used in the present invention is a paint made by mixing mineral pigments such as white clay and adhesives (e.g., casein, starch, latex, polyvinyl alcohol and combinations thereof). Refers to paper coated on one or both sides of base paper (e.g., high-quality paper, medium-quality paper, etc.).
209 per m2), coated paper (coating layer/tn IO per 2? around), light coated paper (coating @/j per m2).
(front and back), and after applying the paint, while the plasticity still remains, it is pressed to a dryer with a mirror finish and dried.
Including cast-coated paper, which has lost its strong luster (for details, refer to the complete paper, ?Rupu Technical Handbook 1/R, 2nd edition 11/r, pages 131 to 134 Sadato, edited and published by the Paper and Pulp Branch Techniques Association) .

This coated paper has a high surface smoothness even when the base paper is thin (cast coated paper in particular has extremely high surface smoothness), so even when the alkaline treatment composition is spread between the rollers, there is no unevenness in the spread thickness. Also, the photosensitive layer, image-receiving layer, and other coated layers coated on this -H have little uneven coating or drying, and furthermore, because the deformation due to heat is small, the uneven coating or drying is small, resulting in image unevenness. can be prevented from occurring.

Preferably, it is 2097 m -200 f/m2 on scale 1.

In the present invention, a coating layer or an image-receiving layer for photographic materials, which will be described later, may be applied directly onto the coated paper ξ-, or one or both sides of the coated paper may be coated with a polymer such as polyethylene. It may be coated or laminated, and if necessary, an undercoat layer may be further provided, and the above-mentioned coating for photographic materials or an image receiving layer may be applied (8. This polymer such as polyethylene may be coated with titanium dioxide or the like as necessary. A white reflective layer may be formed by kneading a white pigment.Also, the preferable range of coating or laminating thickness of this polymer such as polyethylene is from jμ to jθμ, and in particular, a relatively thin layer of less than hiθμ. The effect of the support of the present invention becomes noticeable when the film thickness is ~.

Coachite paper 1'-J described above in the present invention.

When an external support is used for a photosensitive sheet or an image-receiving sheet, the support may be transparent or opaque, but it is preferably one that does not undergo significant dimensional changes during processing. Examples of such supports include cellulose acetate film, polystyrene film, and
Examples include polyethylene terephthalate film, polycarbonate film, baryta paper, and paper whose surface is laminated with a water-impermeable polymer such as polyethylene.

Titanium oxide,
A whitening agent such as barium sulfate may be added, or the above-mentioned whitening agent may be coated on the support.

Furthermore, in order to make it possible to develop the product in a bright room, the support is laminated with polyethylene containing a light-shielding agent such as carbon black, or the support is coated with a water-soluble polymer (gelatin or polyvinyl It is also possible to apply a dispersion dispersed in alcohol (such as alcohol) to provide light-shielding gold. The amount of light-shielding agent added may be adjusted by adjusting t according to the sensitivity of the photosensitive material to be light-shielded, but the optical density is t-1.
0-? - degree is preferred.

A preferred embodiment of the present invention is that the multilayer color photographic light-sensitive material comprises at least seven internal full-image type ln tangent emulsion layers in combination with a dye image discoloring compound on one of seven supports; This is the case for color diffusion transfer photographic elements comprising an image receiving sheet containing at least one image receiving layer per support, and a processing liquid body containing an alkaline viscous processing composition.

This will be described in detail below.

It is preferable to provide a neutralization mechanism in the receiving sheet (between the support and the image receiving L-) or the photosensitive sheet (between the support and the silver emulsion) used in the present invention. The neutralization mechanism is usually
It consists of a neutralization layer and a neutralization timing layer combined therewith (the neutralization timing layer is not essential).

It is preferable to use a film-forming acidic polymer for the neutralization layer, and any such acidic polymer can be used. Examples of acidic polymers include mono-/O-butyl ester of a copolymer of maleic anhydride and ethylene, monobutyl ester of a copolymer of maleic anhydride and methyl vinyl ether, and monoethyl copolymer of tethylene maleic anhydride. Ester, monopropyl ester of the same copolymer, monopentyl ester of the same copolymer, monohexyl ester of the same copolymer, monoethyl ester of the copolymer of maleic anhydride and methyl vinyl ether, mono of the copolymer 11i Zorobyl ester, monobenzyl ester of the same copolymer, monohexyl ester of the same copolymer, polyacrylic acid, polymethacrylic acid,
Copolymers of divine ratio of acrylic acid and methacrylic acid, ``acrylamides or methacrylic acid and other vinyl monomers, such as acrylic esters, methacrylic esters, vinyl ethers, acrylamides, methacrylamides, etc. Copolymers containing acrylic acid or methacrylic acid in various molar ratios, preferably 5o to 9o molar ratios, can be used. Regarding the neutralization layer, US Patent 3.3t2. r/ri, 3.7tj, ♂♂j, 3. r/9,37/, French patent λ, 29o,
It is also mentioned in the T Tata issue. Among them, it is effective to use polyacrylic acid and acrylic acid-butyl acrylate copolymer.

Neutralizing timing layers used in combination with neutralizing r- may include, for example, gelatin, polyvinyl aphrecol, polyacrylamide, partially hydrolyzed polyvinyl acetate, β-
A copolymer of hydroxyethyl methacrylate and ethyl acrylate or acetyl cellulose is used as the main component, and other US patents 3,4 tjJ, trt
No. 3. ≠Ko/, No. 193, 3,711. rlj, 3°tray, &/r, 4t, 009.030
No., Japanese Patent Publication No. 744. ≠7 can also be used. Furthermore, the neutralization timing layer,
For example, U.S. Patent μ, OJ'4, JPV.

0 Otsu/, 41'? No., Japanese Unexamined Patent Publication No. 3-72. It is also possible to use a polymer *'t- which has a large temperature dependence with respect to permeation of an alkaline processing liquid, such as those described in Otsu No. 2λ or JP-A-74T-7F, No. 130.

In addition, in the "neutralized timing layer" that can be used in the present invention, a polymerization product of Uro + Pi which undergoes β-dissociation in an alkaline environment can be used. Showa to-/5'/3'
No. 7, US Patent≠, Co? 7. ≠No. 37, 11. jet
, j, No. 23, 4 II, 20/, No. 117, same g., J
, No. 29.573, JP-A-Shojj-/J/G3r, same-j
&-/4bu No. 211, same! ! -μ/4'70, same jJ
-j113II/issue, same! ≦-10216 No. 17
-/4t/Otsu+p issue, same Tahu y73r3a issue, same 67
-/7ri No. 1111, West German Patent Application Publication ((JLS) Co., ri 10, 27/No., European Patent Application Publication EP31ri j7
kl, Research Disclosure
hINaclosure magazine)%/Iu! , 2 etc. can be mentioned.

The image-receiving layer used in the present invention is preferably a hydrophilic colloid layer containing a polymer mordant.

The polymer mordants used in the present invention include polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing hexacyclic moieties, polymers containing these quaternary cation groups, and having a molecular weight of s, ooo- λoo, ooθ, especially 10,
000-40,0θθ.

For example, US Patent Co.! 4tt, tag number, same 2゜4t
♂gu, gu30, same 3, /4tI, 027, same J, 7! t, I/4 are vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in the specification etc.;
No. J4tj, U.S. Patent No. -r.

No. 301, Dohiro, 273. ? ! No.3, same≠, /ri3,
No. m, No. 11,221.2!7, No. ≠.

Imidazole polymers described in Ko, 2P, j; /jt, etc.; 3,42! , 69≠ issue, same 3゜rr
Polymer mordants capable of crosslinking with gelatin, etc., disclosed in U.S. Pat.
risr, yyj, same, 72/, 112, same 2.
7Yr, Ot3, Tokukai Showa j4t-//jko2, same! Latex-type mordant or aqueous sol-type mordant disclosed in μm/173629, -l Pi-Jgu/26027, JP-A No. 2323aO Specification 1, etc.; US patent, i, rP.

A water-insoluble mordant disclosed in the specification of or: U.S. Pat.
No.) Reactive mordants capable of covalently bonding with the dyes disclosed in the specification, etc.; and US Pat. No. 3,702. tyo issue,
Same j, 711, l'jj issue, same 3,4172.17
No. 12, 3,1111.704-, 3. j37
．． O4t No. 3, 27, No. 717, J, 27/
, No. IIl&', JP-A No. 5o-7/332, same j
No. 3-3032r, same j2-/j! ! Kowo No., same! 3-
/Ko! Same issue! Mention may be made of the mordants disclosed in No. 3-7021 It.

The song, US 11 patent, t7j, 3/, is the same.

rr, 2. Mention may also be made of the mordants described in IRT.

Among these mordants, those that are difficult to migrate from the mordant layer to other layers are preferred, such as those that undergo IJ lux crosslinking reaction, water-insoluble mordants, and latex dispersion (or aqueous sol) type mordants. is preferable.

The non-diffusible dye-providing compound used in combination with the light-sensitive silver halide emulsion layer in the present invention may be any compound that releases a diffusible dye or its precursor image-wise as a result of development, e.g. Dye-releasing redox compounds are preferred, although dye-releasing non-diffusible couplers can also be used. Dye-releasing redox compounds are negative-type (
negative working) as well as positive working (p
ositive working), but a negative type is preferred. A positive image is obtained by combining a negative-working dye-releasing redox compound with a total direct reversal emulsion.

The dye-releasing redox compound used in the present invention can be represented by the following general formula.

Y-1) Specific examples of Y are given in US Patent 3. ri, 2r, 3F, same 3.
No. 993.43, same da, 074, tλri no., same≠
, /J-λ, /33 issue, same≠, θoyo, 4tat issue, same +, 0! ! , No. 312, 4j, / PI.

No. 235, same issue, /7ji,, 29/ issue, same 4t, /4t
222, 3. Hiroshi ♂4, No. 713, same 3゜≠≠
3. P-Hiroshi 3, 3, 7! /, 4tO6, 3.4t
≠No. 3,939, 3. ≠≠3. Tada θ, same J, A
, 2F, 9j, No. 2, No. 3,910,4179, No. 13.713, No. 13.713, No. 3,910,4179, No. 13. No. 7, No. 4
No. 1,271,7!0, 4t, /39'.

No. 37, same≠2.21♂,! A7, same 3. ≠2/,
94 Hiro issue, Dokei, / Tata, 3j! No., same≠.

/Pri, jj4 issue, same≠, /31. Octopus No. 2, Octopus II
, No. 334, 322, II, /39, 31? No., Tokukai Shojj-! No. 10736, same O/-10μ3≠3, same! ≠-/30/λλ issue, 413-/10? , No. 27, No. 4-/264-, No. jJ-/A/3/, No. j7-
≠Ohiro No. 3, same! 7-tj.

No., jt7-2073j, same! 3-toi No. 3,
It is listed in tx-itit3≠λ issue, tx-itit3≠j issue, tx-itit3≠j issue, etc.

Of Y in the negative dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (N-fi
Examples of the t substituent include a group derived from an aromatic hydrocarbon ring or a heteroc1 ring.

When a positive dye-releasing redox compound is used, it is known as a diffusion-resistant electron donating compound (El) compound).
or its precursor in combination. Examples of El) compounds include, for example, US%
It is described in Kihiro, Kot 3, 3, No. 3, Kot 3, No. 171.710, JP-A-74-131734, and the like.

On the other hand, specific examples of the dye represented by D in the above general formula are described in the following literature.

Example of yellow dye 7? - US Patent 3. ! 77. No. 200, No. 3,302゜/P, No. ≠, No. 0/3,433, No. 3, 2, Hiro! , Oko? No., same≠, / Ta Otsu, No. 609, Dokei.

/3'? , No. 313, 4≠, /ri J, No. 95F2, 4
t, /44f, A! / issue, 4t, /4#, 44'j
No., same number, 33t, 3λλ; JP-A-61-//Geta 3
No. 0, Room 74-7107 Research Disclosure/
7JjO (15'7F), same /4447j (/P77
) Items listed in item ).

Example of magenta dye: US Patent 3. μm3,707, same 3. H0゜571, same 3. 32.311θ, same 3. ri3/,/Gugu issue, same J, P32,301, same 3゜rij≠,≠76,
4G, λ33, No. 237, 4G, λ11. jOP, Dohiro, λto, Wara, Dodo A, IA2. rri No. 7, 11
．． ．． No. 207, 1011, 4G, -♂7.2 Octopus No.; Tokkai Shoj, 2-10t, No. 727, same! r2-10A72
No. 7, same j3-, 23. t, No. 21, zs-JJ,
No. 1041, It-73, 017, tJ-71O
Same as tO! What is listed in j-/J Hiro issue.

Example of cyan dye; US Patent 3. Hiroshi, 2. No. 72, 3. riλri.

7tO issue, Dogu, 0/J, Otsu 3j issue, Dokei, 2tr, 6
No. 21, 11. /7/, No. 2264, Dokei.

2412.173j No. ≠, / Guko, ♂ri No. 7, I
I, /91.9!7'fi issue, same 11. /IIt7. j
No. ll'i', No. 4LJ', No. 44-; British Patent/, 33/.

i3r; Tokukai Shoj≠-99 Ko3 No., sameyoichiza rλ7
No., same j3-≠7t13, same ta 3-/4t33λ3, same j4 one tatag 3/, same j4-7/θ4/:'
Ei-Lotupa patent ('KPC>z3゜037, same j3
．． 04tO issue; Research Disclosure (Res.
search I)isclosure)/7. Otsu 3
0 (/7F), and /4. ≠Things described in 7j (lli 77) issue.

Further, as specific examples of other dye-providing compounds, the following can also be used.

e l-1 (in the formula, 1) represents a dye or a precursor thereof as defined above. ) Please refer to U.S. Patent No. 3,71, ≠♂, μ, 09
&', 7♂ No. 3.

The coating amount of the dye-providing compound used in the present invention is approximately /X1
A value of 0-' to /X10-'' mol/712 is suitable, preferably 0 to 2x10-3 mol/m2.

In the present invention, as a photosensitive silver halide emulsion, 2 l
− Negative working emulsions and internal latent image direct reversal silver halide emulsions are used, which emulsions include silver chloride, silver bromide, silver chlorobromide,
A hydrophilic colloidal dispersion of silver chloride, silver chloroiodobromide, or a mixture thereof, the halogen composition of which is selected depending on the intended use and processing conditions of the light-sensitive material, but with an iodide impregnation of 10 moles. % or less, silver bromide, silver chloride or silver chloroiodobromide with a chloride impregnation of 16% or less is particularly preferred (7%).

The crystal shapes of silver halide grains are cubic, octahedral,
In addition to spherical regular particles such as /Ghedron, Research ζ Disclosure (几68earchDtscloau
re) &22!3tA, Jan, /Det3 and the aspect ratio as shown in Japanese Patent Application Laid-Open No. 101jλr! The above tabular grains are also included.

Endocrine type silver halide emulsions are emulsions processed by doping metals such as copper, cadmium, lead, and lead as different elements into the crystal grains, and photographic properties such as reversibility are improved by such doping processing. It also includes emulsions such as those described in U.S. Pat.

Direct positive f@! using these latent type emulsions! A nucleating agent is used to form the nucleating agent.

Regarding internal latent image emulsions and nucleating agents used in this field.
Research Disclosure (Re5search)
I month Blc) sure ), /j/volume/116
2 (Published /7/monthly/year) No. 7 is described in the left column of page J2, line to page 7R, left column, line T, which can be used in the present invention.

In the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength evening light, green light, red light or infrared light using a sensitizing dye. Regarding spectral sensitization, especially for internal latent image type, please refer to the above Research Disclosure.
What is described in the 7th left column of /j/12 from line 1 to line 2 of the right column of the same page can be used in the present invention.

The thickness of the photosensitive emulsion layer is o, t-t, oμ, especially o, t-
Hiroshi, Oμ, and the coating amount of silver halide grains was 0. /
~3fl/m, preferably O2,2~/, 11
It is 7m.

Any silver halide developer can be used in the present invention as long as it is capable of cross-oxidizing the dye-providing compound. Such a developer may be included in the alkaline processing solution or in an appropriate layer of the photosensitive sheet.

Examples of the developer used in the present invention are as follows.

Hydroquinones, aminephenols, phenylenecyabane, and pyrazolidinones described in U.S. Pat. Dihydroxymethyl-3-pyrazolidinone, /-p-)liru-7-methyl-Hiro-hydroquinemethyl-3-pyrazolidinone, /-(l'-methoxyphenyl)-μmmethyl-μ
m-hydroxymethyl-3-pyrazolidinone, /-phenyl-Hiro-methyl-≠-hydroxymethyl-3=pyrazolidinone], etc.

Of these, black and white developers (especially pyrazolidinones) are particularly preferred, as they generally have properties that reduce staining in the image-receiving layer better than color developers such as phenylenediamines.

The processing solution contains bases such as hydroxide, potassium hydroxide, sodium carbonate, and sodium phosphate.
It has an alkaline strength of H2 or higher, preferably //, 1 or higher. The treatment solution may contain antioxidants such as sulfite, ascorbate, and piperidinohexose reductone, and may also contain a silver ion concentration regulator such as potassium bromide. . It may also contain viscosity increasing compounds such as hydroxyethyl cellulose and sodium carboxymethyl cellulose.

The alkaline processing solution may also contain a compound that promotes development or dye diffusion (for example, a compound such as benzyl alcohol).

In addition, the alkaline processing liquid contains a white pigment (for example, l''i U
or Z n 02) may also be contained.

Preferably, the Jt-alkaline treatment is contained in a pressure rupturable container.

In multilayer color photographic emulsions, a silver halide emulsion and a dye-providing compound are combined and the intended purpose is 11. The combination of the color sensitivity of the silver halide emulsion and the spectral absorption of the dye image is appropriately selected depending on the color reproduction desired. To reproduce natural colors by the subtractive color method, a photosensitive sheet consisting of at least two combinations of an emulsion with selective spectral sensitivity gold in a certain wavelength range and a dye-donating compound with selective spectral absorption in the same wavelength range is required. used. In particular, photosensitive sheets containing a combination of a growing silver halide emulsion and a yellow dye-providing compound, a combination of a green-sensitive emulsion and a magenta dye-providing compound, and a combination of a red-sensitive emulsion and a cyan dye-providing compound are useful. The combination of these emulsions and dye-donating compounds may be applied in layers in a face-to-face relationship in a photosensitive sheet, or each grain (with the dye-donating compound) and silver lokenide particles may be coated in the same manner. present in particles), mixed and applied as a single layer.

Also, in the middle I- of the photosensitive sheet, US Patent Gu, 3λ-co
6-3. Gold may be added to the silver halide emulsion as described in Otsu No. 3j.

In the film unit of the present invention, after exposure of the photosensitive element, when the film unit is taken out from the camera, the film unit (in which the photosensitive element and the image receiving element are superimposed) is passed between a pair of juxtaposed suppression members. It is preferable to develop the exposed silver halide by completely destroying the container disposed between the photosensitive sheet and the image-receiving sheet, and releasing the first liquid therein and spreading it over the entire surface.

Another preferred embodiment of the present invention is a silver salt diffusion transfer photographic light-sensitive material, and in the process of processing these light-sensitive materials to form a silver image, a developer may be present in the light-sensitive sheet or in the processing composition. As the developer, a benzene- or naphthalene-based organic compound having a hydroxy group and/or an amino group at the para or ortho position, such as hydroquinone, tert-butylhydroquinone, p-aminophenol, etc., is used.

Furthermore, US% Pestle J, 41! , reductic acid as described in ≠≠θ and U.S. Pat. No. 3,730.71! Preferably, α,β-enediols such as those described in the above are used. Additionally, U.S. Patent 3. ．． 2r7. /, 2
Hydroxylamine developers such as those described in No. J and No. 3, 293, 03 are particularly preferably used.

The amount of developer used is 100 f of processing solution (t) 0, / f
~(It is preferable to contain 70f, and /~20? is most preferable.

Further, as a developer, the /-aryl-3-pyrazolidino/compound described in the invention in Japanese Patent Publication No. 3R10 may be used in combination with the above developer.

Silver halide solvents may be present in the processing composition, the photosensitive sheet and/or the image receiver. Among these, treatment compositions are most preferred. U.S. Patent Co., 167°274! No., same co.
137. The cyclic compounds described in Core No. J and Core No. 2゜117.27 No.
Preferred examples include urazol and t-methyluracil.

Further preferred are alkali metal thiosulfates, especially the sodium or potassium salts, and also as described in U.S. Pat. , 9 Octopus No. 3,974. Hiro 7, 4t, 009. /47
No., same≠, 032. j31, 4t, oaA, ztr
No. 44, 04'7, Re No., Dohiro, 04t7
．． the law of nature! ! No., same, 107. /7 Otsu issue and Japanese Patent Application Publication No. 1973
7-jJO's disulfonylmethane compound and U.S. Pat.
/ Kot, ≠! No. 1, II, /10. Ko λr, same μ,
λ//,! Jri issue and same II, 2//,! No. 62, dihydroxypyrimidine compounds having a thioether group, and US Pat. No. 4t, 23-7. Bu77, Same μ, Kobu7
．． It can be selected from the aminothioethers of λj≠ and Dokei, λ67.256. These can be used alone or in combination; if two or more types of cyclic imide compounds or dihydroxypyrimidine compounds with thioether groups are used together, white crystals may precipitate on the surface even if stored for a long time. This has the advantage of eliminating the

The amount of silver halide solvent added is determined by the processing composition io.

-Ko? - It is preferable to contain o, i to 30f per V, and 0.
1t~10? is most preferred.

Processing liquid used in the present invention When applied by distributing it as a thin layer between a photosensitive sheet and an image-receiving sheet that have been combined, the processing liquid contains a polymeric film-forming agent, a thickening agent, and a thickening agent. Preferably, it contains a sticky agent. Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful for this purpose,
They are included in the processing solution at a concentration effective to provide a suitable viscosity for the 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,
A stabilizer or the like may also be included. In particular, the inclusion of oxyethylamino compounds, such as triethanolone, is useful in increasing the shelf life of processing solutions, as described in U.S. Pat. No. 3,61,113.

The processing liquid as described above is preferably contained in a breakable container. Regarding breakable containers and their materials,
Any known h can also be used, such as, for example, US Patent 3.0! t, geta/issue, same 3.
0ta Otsu, No. 419.2, No. 3, /73,110, No. j
, 7!0.707, same? , 13! ,! It is described in detail in No. I1, No. 4t, No. 303.710, No. 303.7j1 of Dokei, etc.

The image-receiving notebook in the present invention includes an image-receiving layer containing a silver precipitant. Such image-receiving sheets can be prepared by coating an optionally subbed support with a coating solution of a suitable cellulose ester, such as cellulose diacetate, preferably in which a silver precipitant is fully dispersed. The obtained cellulose ester layer is subjected to alkaline hydrolysis to convert at least a portion of the cellulose ester in the depth direction into cellulose. In a particularly useful embodiment, the silver precipitant and the cellulose ester in the underlying layer that did not undergo hydrolysis, Example 1-1: Hydrolysis of the cellulose ester layer containing lactose diacetate. The missing portion contains seven or more mercapto compounds suitable for silver transfer images. Such mercapto compounds are utilized during imbibition by diffusing from the position where they are initially placed. This type of image receiving sheet is used in U.S. Patent No. 3,607.2&'? It is written on the number and is counterfeit.

Examples of suitable silver precipitants include heavy metals such as iron, lead,
Lead, nickel, cadmium, tin, chromium, copper, cobalt, especially precious metals such as gold, silver, platinum and palladium. Other useful silver precipitants are sulfides and selenides of heavy metals, especially mercury, copper, aluminum, zinc, cadmium, cobalt, silver, lead, antimono, bismuth, cerium, magnesium, gold. , sulphides of platinum and palladium, and selenides of lead, zinc, antimony and nickel, among others gold. Regarding the function of materials such as silver precipitants in the silver salt diffusion transfer method,
For example, it is described in US Pat. No. 77, No. 667.

Furthermore, it is preferable to provide an intermediate layer between the image-receiving layer and L- containing a toning agent and a stabilizer. Middle class and 1-te, t
Examples of the t, t, and -h materials include gum arabic, polyvinyl alcohol, and polyacrylamide.

Further, it is 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 spreading the treatment liquid. Preferred release layers include gum arabic, hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, polyacrylamide, and sodium alginate, as well as US Pat.
No. 72,024, J.? , 20. ? Mention may be made of those described in No. Tata and British Patent No. 360.6jJ.

In the photosensitive silver halide emulsion used for silver salt diffusion transfer, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as the silver halide. Preferred counterfeit silver halides are silver iodobromide or silver iodochlorobromide containing silver iodide of less than /θmolti.

Particularly preferred is silver iodobromide containing silver iodide at 3 to 10 molty soil.

The average grain size of the silver halide grains in the light-sensitive emulsion (expressed as the grain diameter in the case of spherical or approximately spherical grains, and the lengthwise total grain size in the case of cubic grains, expressed as an average based on the projected area) is particularly important. No, but less than 3μ is preferable.
Further/, jμ or less is preferable, but particularly preferable is 0
．． r~7.2μ.

The particle size distribution may be narrow or wide.

The silver halide grains in the light-sensitive emulsion may have an equiaxed crystal form such as a cube or an octahedron, or may have an irregular crystal form such as a spherical shape or a plate shape. It may have a composite form of these crystal forms, or it may consist of a mixture of particles of various crystal 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. Further, -34t- particles may be used in which a latent image is mainly formed on the surface, and particles in which a h0 latent image is mainly formed on the surface are preferable even if the latent image is mainly formed inside the particle.

The thickness of the photosensitive I'L emulsion is o, tr, oμ
, especially 0.1 to 5oμ, and the coating # of silver halide grains is 0.1 to 5oμ. /~39/m2, preferably Oo, 2~/, 6
It is 97m.

The light-sensitive emulsion is prepared by a conventional method using a silver halide photographic emulsion (-), and chemical sensitization and spectral sensitization are performed as necessary. It contains auxiliary agents, antistatic agents, etc. Also, a vehicle such as gelatin is used for 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. The exposure time is from 171,000 seconds normally used in cameras to 7
Exposure times of seconds, of course, but also exposure times of / / / 000 seconds, such as those using xenon flash lamps or cathode ray tubes.
Exposures of /io' to //106 seconds can be used, or longer exposures can be used.

If necessary, the original spectral composition used for exposure can be fully adjusted with color filters. 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 bonding method of each element for forming a film-knit by combining the photosensitive sheet, image-receiving/processing composition, and processing composition as described above, see, for example, Neblettes, Handbook of
Photography Antliprography (HA, N plate)
H(J(-JK (n' yen l0TO-Gi also APHY AND REPlt(JGRAI'HY),
7th edition, 212-2t! The sometimes preferred embodiments are described in detail in US Pat. No. 3,360,727, which may be referred to here.

(Example) Example 1 An image-receiving sheet having the following structure was prepared on the paper support shown in Table 1.

Back (tllll: (a) Carbon black≠
, θy/m2 gelatin, light shielding layer of oy/m2, (b) titanium oxide, Oy/m2, gelatin t, white layer of oy/m2.

(c) Gelatin 0. A protective layer of Aj’/m2.

They are coated in the order of (a) to (c).

Image-receiving layer side: (1) A neutralization layer containing 2λ/m2 of acrylic acid-butyl acrylate (molar ratio: 2) copolymer with an average molecular weight of jo and ooθ.

(2) cellulose acetate with acetylation degree j/, 3% (the weight of acetic acid released by hydrolysis is 0.j/3f per sample IP), and styrene-maleic anhydride (with an average molecular weight of about 10,000). molar ratio /: /) copolymer in a weight ratio t s = l 3,
Neutralization timing layer containing y/m2.

(31 styrene-butyl acrylate -Acrylic acid-N methylol acrylic acid Weight ratio of lylamide≠゜, 7/Hiroshi x, emulsion polymerization at a ratio of 3/p/lI Polymer latex and methyl Methacrylate/acrylic acid/N -Methylol acrylamide Quantity ratio? Emulsion polymerization at a ratio of 3:3:≠ The solid content of polymer latex Blend so that the ratio is 6 to μ The total solid content is t, including A17m2. layer.

(4) The following polymer 3. oy/m2 and ze Latin 3,017m2 as coating aid as 3 t- (n,,=30) Image-receiving layer coated using

(5) Coating gelatin o, l, y/m2 (protective layer).

Photosensitive sheet A photosensitive sheet was prepared by coating each layer on a polyethylene terephthalate transparent support as follows.

Pack side: (a) Carbon black 4t, oy/m
2 and gelatin 2.0 to 7.2.

Emulsion layer side: (1) The following cyan dye-releasing redox compound 0.1I4tf/m2, tricyclohexyl phosphate 0°O 17m2.2, pentadecylhydroquinone 0°oo 17m2, and gelatin 10, fry/ layer containing m2.

(2) Red-sensitive internal latent type FM tangent silver bromide emulsion (silver amount: 1
．． o3y/n>2, gelatin/, -2y/m2), the following nucleating agents o, o hiroku/m2 and λ-sulfo J--n-pentadecylhydroquinone sodium salt θ,/3p/m2. Contains a red-sensitive emulsion layer.

(3), 2. Layer containing t-di-t-pentadecylhydroquinone O0≠3y/fur2, trihexyl phosphate 0.1 17 m2 and gelatin o, +y/m2.

(4) Magenta color release of the following structural formula ■ Output redox compound (o, 2ty/ m2), magenta dye with structural formula ■ −≠　l− Release redox compound (0, // 17m2), l-licyclohexyl Phosphate (0,01y/m2) 1 ．． 2. ! -G-t-pentadecylha Hydroquinone (o, oo 17m2) and gelatin <0.9 tl/m2) A layer containing.

Structural formula I (5) Green-sensitive green-sensitive inscribed inverted silver bromide milk agent (0.12y/m2 due to silver, Gelatin 0079/m2), layer (3) Same nucleating agent (o, o3■/m2) and kosuruho j-n-pen Tadecyl hydroquinone natri Contains lamb salt (0, Or 17m2) green-sensitive emulsion layer.

(6) Same layer as layer (3).

Yellow dye-releasing redox compound with the following structure (0,j3y/m), tricyclohexyl phosphate (0,/31/m2), 2.!-di(-intadecylhydroquinone (o,o/gy) /m2) and gelatin (o, yy/m2).

-Hiroshi 3- (8) Blue-sensitive internal temperature direct inversion silver bromide emulsion (silver amount/0.17 m2, gelatin/77/m2), same nucleating agent as layer (3) (0.041 m2). /m2) and norsulfo-t-n-pentadecylhydroquinone strium salt (0.07y/m2).

(9) Gelatin 1. including oy/m2 layer.

The photosensitive sheet was transferred with a reflection density of 0. After uniform exposure so that the image is 2-≠ ≠- jμ, the image-receiving sheets shown in Table 1 are stacked on top of each other, and the following processing solution is spread between both sheets to a thickness of 2-≠ ≠- jμ. The help of rollers was carried out with itch). Processing is performed by jj'c, processing f11!
rear? The photosensitive sheet and image receiving sheet were peeled off in θ seconds. The results are shown in Table 1.

= ≠! - From Table 1, it can be seen that when the coated paper of the present invention is used, the occurrence of image unevenness is significantly reduced.

Example 2 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 (Iodine content!

Jmolti) was obtained. The average diameter of the silver halide grains contained in this emulsion was O.tamicron.

The emulsion/11ji contained 0.6 moles of silver halide. Collect 19 of these emulsions into pots,
! It was dissolved in a constant temperature bath at θOC.

Ortho-sensitizing dye 3-(yo-chloro 2-[
λ-ethyl-3-(3-ethyl-cobenzothiazolinylidene)propenyl]-3-penzogizazolio)prono-Q-sulfonate, panchromatic sensitizing dye (≠-(co[(J-ethylbenzothiazoline-(2) -Iriden)-
10 rnl aqueous solution by weight of 2-methyl-7-propenyl]-3-benzothiazolio)phthanesulfonate) and ≠-hydroxy-6-methyl-≠ 7--/, 3,3a, 7-titrazaindene, cohydroxy- ≠ 10 ml of sodium t-dichlorotriazine bath solution.
Furthermore, sodium dodecylbenzenesulfonate 7-1
- 7 oml of shaded water bath liquid, Ribo MO, 7 oml of methanol solution/Oml at 100°C were added and mixed and stirred at 1IO0C. This finished agent was applied to a polyethylene terephthalate film base containing titanium dioxide which 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.jμ) was added to the aqueous gelatin solution and coated to a dry film thickness of 7 microns. The amount of silver applied is 0
．． It was 377m2.

Image-receiving sheet An image-receiving sheet was prepared using the support shown in Table 2 with the following configuration.

Image-receiving layer side cellulose acetate) (degree of acetylation, t4'%) it
y and styrene-maleic anhydride copolymer/, 2y or -
Reference r- A solution of 72 acrylic acid-alkyl acrylate copolymer dissolved in 270 ml of acetone and 30 ml of methanol! It was applied to a thickness of uml/m2 and dried.

On top of this, a 10% cellulose acetate acetone solution of 31-diphenyl-/, ≠-dimercapto JH+AH-2+3a +j +Aa-tetraza-antalene (0,0!P/m") was added to a dry film thickness of 10 y/m". I applied it to make it look like this. Furthermore, on top of this, polyacrylamide
% aqueous solution, dimethylol urea (j%) aqueous solution and acetic acid (1%
0%) were added and mixed at j%, i, :ir concentrations, respectively, and coated at a coating thickness of 2jml/m2. Furthermore, on top of this, add 3% cellulose acetate in acetone/methanol (
1) Apply a solution in which palladium sulfide is finely dispersed in the bath solution. This coating solution contains / , 2j x 70-6 mol/
7-phenyl-j-mercaptoimidazole was contained in a coating amount of m2. The dry film thickness was o.rμm. Add the following alkaline solution to this coating /Irn1/
An image receiving sheet was prepared by coating the film at a ratio of m 2 and washing with water and drying. The above palladium sulfide dispersion was prepared using 3% acetone/methanol (9//) of cellulose acetate.
A methanol bath solution of 7 x 10 -3 mol of sodium sulfide and a methanol bath solution of 7 x 10 mol of sodium chloride (sodium chloride) were added to the mixed solution and stirred thoroughly.

Back side a) Carbon black r, Oy/m21 Gelatin
r, oy/m2 light shielding layer b) Titanium sulfide 10. Oy/m2, gelatin 1, o
A white layer of y/m2 C) Gelatin/A protective layer of oy/m2 was applied to each of the above sheets.

Treatment liquid potassium hydroxide (rz section) Kotoy titanium dioxide 3F uracil
41jf2-methyluracil
rejy hydroxyethyl cellulose
70y zinc oxide
10yN,N-bismethoxyethylhydroxylamine toytriethanolamine 7ytetrahydropyrimidinethione 0.4tyN,≠-dimercaptopyrimidine 0.3oiAnpropylthiouracil
Add 0.3jp water
2Kg of the photosensitive sheet was coated with Gray (reflection density 0.3~0).
The image-receiving sheets shown in Table 2 were stacked on top of each other, and the processing solution was spread between the two sheets to a thickness of 3 μm. Process / Yo uC and 2!0 (:, after expansion /j0C, 60 seconds,
2100. In the case of 4t! It peeled off after a few seconds.

−j　／−

Claims (1)

[Claims] A photosensitive sheet having at least one photosensitive silver halide emulsion layer on a support, an image receiving sheet having at least one image receiving layer on another support, and an alkaline treatment developed between these two sheets. A diffusion transfer photographic material comprising a composition, wherein at least one support is made of coated paper.