JPH01167836A - Method for preserving silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To improve the shelf-life stability of the title material by preserving a prescribed photosensitive material in the presence of a drying agent and/or an antioxidant. CONSTITUTION:The silver halide photosensitive material contg. a water insoluble basic metal compd. (such as zinc hydroxide) and a reducing agent (such as a reducible dye supplying compd.) is preserved in the presence of the drying agent (A) and/or the antioxidant (B). And the drying agent (A) is composed of a silica gel, etc., and the antioxidant (B) is composed of a mixture of ferrous sulfate and an iron powder, etc. The drying agent and the antioxidant are preserved by wrapping them with a paper, etc., and enclosing a wrapped matter together with the photosensitive material in a bag made of polyethylene, etc., while shielding the light. And, an inactive gas such as a gaseous nitrogen, may be used as the antioxidant (B), and the photosensitive material may be preserved by degassing.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for preserving a silver halide photosensitive material containing a basic metal compound that is sparingly soluble in water.

<Prior art and its problems> European Patent Publications Co., Ltd. and Toh No. 2, etc. contain a basic metal compound that is sparingly soluble in water in a silver halide photosensitive material.
A complex-forming compound is contained in a treatment solution or a layer on another support such as a dye fixing material, and the basic metal compound and the complex-forming compound are reacted using water as a medium.
A method of forming an image by increasing -i is disclosed.

This method can maintain the PTI of the image forming system near neutrality before development processing, is very easy to handle, and can quickly obtain images, but some of the basic metal compounds in the photosensitive material Because it dissolves, the film pH is slightly higher than that of ordinary photosensitive materials that do not contain basic metal compounds. For this reason, in photosensitive materials containing a reducing agent, the reducing agent is likely to be oxidized by the influence of moisture and oxygen during storage, resulting in an increase in capri and fluctuations in sensitivity and gradation.

In order to improve this problem, JP-A-4.2-tr73μ
No. 7 discloses a method of incorporating a water-soluble salt of a metal ion constituting the basic metal compound into a photosensitive material in addition to a basic metal compound that is sparingly soluble in water. - Further improvements are needed for photosensitive materials that share reducing agents that are easily oxidized, such as pyrazolidones.

<Object of the Invention> An object of the present invention is to provide a method for stably preserving silver halide photosensitive materials that is simple and suitable for rapid processing.

<Disclosure of the Invention> For the purpose of the present invention, a silver halide photosensitive material containing at least a slightly water-soluble basic metal compound and a reducing agent on a support is stored in the presence of a desiccant and/or an antioxidant. This was achieved by

<Style composition of invention> The physical structure of the present invention will be explained in detail below.

As the desiccant used in the present invention, both known chemical desiccants and physical desiccants can be used.

A desiccant agent on the handling top is preferred.

Typical desiccant agents are described in Kagaku Daijiten Vol. 1, page Aj 7 (Kyoritsu Shuppan, 7th edition). A preferable desiccant has a W value (the number of water remaining in the air Il dried by the desiccant) of 10 or less, more preferably 1 or less. Furthermore, any of neutral, acidic, and basic desiccants can be used, but neutral desiccants are preferred.

Preferred drying agents include magnesium perchlorate, activated aluminum, anhydrous calcium sulfate, silica gel, magnesium oxide, calcium oxide, calcium carbonate, anhydrous calcium chloride, anhydrous zinc chloride, and the like.

In the present invention, the desiccant may have any particle size or shape, but preferably has a large surface area in order to increase the rate of moisture absorption. It is also possible to use a combination of different types. The desiccant is used to control the humidity of the storage environment for photosensitive materials. %R)l
Especially below! It is preferable to use the amount necessary to reduce the RH to 0%RH or less.

Oxygen absorbers are effective as antioxidants used in the present invention. Oxygen absorbers include sulfites (e.g. sodium sulfite, sodium bisulfite, magnesium sulfite, etc.), dithionites (e.g. sodium dithionite, etc.), sulfinates (sodium Hensensulfinate, etc.), metals, or metals. salts (e.g. iron, zinc, nickel, ferrous sulfate, etc.), ascorbic acid or its salts (e.g. sodium ascorbate, etc.), and other compounds with reducing power (hydroquinones, 3-pyrazolidones, hydrazines, hydrazides, borane/amine complexes, aminophenols, catechols, lignins,
Tannins, Engineering 17 Fluhin + [i, p-phenylenediamines, hydroxytetronic acids, μm amino-!
-pyrazolones, etc.). Also, T, )i, J
Written by ames @The theory of th
e photography process” u
Reducing agents described in Kota/~3J, p. 1 can also be used. A plurality of these reducing agents may be used in combination. The antioxidant is used in an amount sufficient to reduce the amount of oxygen in the storage environment of the photosensitive material.

The desiccant and/or antioxidant described above (excluding the inert gas described below) are used in such a way that they do not come into direct contact with the photothermographic material. In other words, it is not built into the photosensitive material, but placed outside it. For example, there is a method in which the desiccant and/or antioxidant are placed in a bag and enclosed in a photosensitive material packaging bag.

An example of a separate antioxidant used in the present invention is an inert gas. The inert gas mentioned here is one that does not cause oxidation of the components in the photothermographic material. Preferred inert gases include helium, neon, argon,
Examples include rare gases such as krypton, nitrogen gas, and carbon dioxide gas. These inert gases are used by being sealed together with the heat-developable photosensitive material in a packaging material with excellent water vapor and oxygen barrier properties (so-called inert gas lt exchange method). Also,
The present invention also includes deaerating and storing in a so-called vacuum chamber.

Although the effect of the present invention can be achieved by using only 10,000 of the desiccant and antioxidant, it is preferable to use both in combination because the effect becomes greater.

Examples of basic metal compounds that are sparingly soluble in water used in the photosensitive material of the present invention include water solubility at 200C (water ioo
such as carbonates, phosphates, silicates, borates, aluminates, hydroxides, oxides, and basic salts with a gram of substance dissolved in g Examples include double salts of the compound. Among these, those represented by the formula TmXn are preferred.

Here T is a transition metal, such as Zn, Ni, Co, Fe
%Mn, etc., and X represents an ion that can act as a counter ion to M that appears in the explanation of complex-forming compounds described later in mineral water and exhibits alkalinity, such as carbonate ion, phosphate ion, silicate ion, Represents borate ion, aluminate ion, hydroxy ion, and oxygen atom. m and nF
s,, respectively, are integer representations such that the valences of T and X are balanced.

Preferred examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg(COa)2), magnesium oxide,
Zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate , magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate, basic zinc carbonate (, zZnCOa・JZn(
OH)2 ・t+20), basic magnesium carbonate (j
MgcO3°Mg(OH)z・3H20), basic nickel carbonate (NiCOs・λN1(0H)2)% basic bismuth carbonate (Bi2(CO3)02・H2O), basic cobalt carbonate (λCoCO3・3Co(OR) 2),
Aluminum magnesium oxide.

Among these compounds, uncolored compounds are particularly preferred.

The complex-forming compound used in combination with the photosensitive material in the present invention is a complex salt having a stability constant of 1 or more per layer gK with the metal ion constituting the basic metal compound that is sparingly soluble in water. It is.

These complex-forming compounds are described, for example, by N. E. Martin, R. M. Smith (A, E.).

Martel 1, R, M, Sm1th), “Critical Stability Constance (Criti...
calStability Con5tants)+Volumes 1-5”, Plenum Press
s) European Patent Publication λ/0, ttOAλ, US Patent 3I Co. 10. sPt, etc., and any compound can be used.

When adding a basic metal compound that is sparingly soluble in water to a photosensitive material, the layer to which it is added may be either an emulsion layer or an intermediate layer.Also, it may be added divided into multiple layers, or concentrated in one layer. Alternatively, the complex-forming compound may be supplied by being dissolved in a hydrophilic solvent such as water contained or incorporated in the dye-fixing material or a processing solution such as an activator solution developer. Basic metal compounds are disclosed in JP-A Showa Tata/No. 7 Hirorio,
It is desirable to contain it in the form of a fine particle dispersion prepared by the method described in Mukaiyo 3-702733, etc., and the average particle size thereof is preferably 0.0 μm or less, particularly 1 cj μ or less.

In the present invention, water contained in the photosensitive material (the amount of the slightly soluble basic metal compound added depends on the compound type, the particle size of the releasable metal compound, the complex formation reaction rate, etc.); It is appropriate to use an amount of to11 or less in terms of weight, and more preferably a range of o, oix*% to aO weight% is useful.

The photosensitive material used in the present invention basically has a photosensitive silver halide, a basic metal compound that is sparingly soluble in water, a reducing agent, and a binder on a support, and if necessary, organic metal hydrochloric acid. It is possible to contain a coloring agent, a dye-donating compound (such as i, which may also serve as a reducing agent as described later).The same JIl+lC is often added to these components, but if they are in a state where they can react, they can be added separately. It can also be added in separate layers.For example, if a colored dye-donating compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented.Reducing agents are built into the light-sensitive material, but for example, after processing. A portion of the dye may be supplied from the outside by dissolving it or diffusing it from a dye fixing material described below.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three different layers are used in combination with silver halide emulsion layers sensitive to light in the color range.

For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials.

Further, each of these photosensitive layers may be divided into 2/ii or more if necessary.

The photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer.

The photosensitive materials used in the present invention include those for ordinary wet processing;
It also includes those for heat development.

The silver halide that can be used in the light-sensitive material of the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

The silver halide emulsion used in the light-sensitive material of the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a former fogging agent. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. The particle size is 00l-λμ, especially 0.2-1. jμ is preferred.

The crystal habits of silver halide grains are cubic, r-hedral, l-particulate,
It may be in the form of a plate with a high aspect ratio or in any other form.

In terms of appearance, U.S. Patent No. Hiroshi, Zoo, G26'gH
Column o, same No. ts, tar, oxi issue, IJ -F -f
・Disclosure magazine (hereinafter abbreviated as RD) 17
Q Kota (17th year), Tokukai Sho Otko 2!3/zyst
Any of the silver halide emulsions described in '4 can be used.

Although the silver halide emulsion may be used unripe, it is usually chemically sensitized before use. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-42-2J3/!2).

The coating density i of the photosensitive silver halide used in the present invention ranges from 1 da to 10 9 /rn in terms of silver.

The silver halide used in the light-sensitive material of the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

In terms of membership, US Special iFF No. ≠, A/7. ．． 2J'7, JP-A-19-1101! TO issue, same to-ipozJ
J No., R1) / 70λri (1ri7 in the year) 1.2-1
Examples include the sensitizing dyes described on page 3.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, fF 3rd.Is/!.

6da No. 1, % Gansho 61-Coco 62 Yuhiro No. 2 These sensitizing dyes may be added to the emulsion at or before chemical ripening, or as described in U.S. Pat. ,ir
It may be carried out before or after nucleation of silver halide grains according to No. I, YZT, No. 221,444. Appendix 7XIf! t is generally on the order of lo-8 to 10 moles per mole of silver halide.

In the photosensitive material of the present invention, particularly in the heat-developable photosensitive material, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include US FF No. μ, 200.

tλ No. J ~! There are benzotriazoles, fatty acids and other compounds described in 38y11 and the like. Also, Tokukai Sho 4
0-/73ko3! Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylbrobiol, described in No. 1, and acetylene silver, described in JP-A-47-24C90μμ. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0°0/7
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 101n9 to 109 in terms of silver.
/rn is appropriate.

Various antifoggants or photographic stabilizers can be used in the photographic material of the present invention. For example,
RD/74guj (/ri7 in 2016) Ko Hiro~ko! Azoles and azaindenes listed on page JP-A-Sho! Tar/6141μ
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 2, or JP-A-Sho! 2-/Ill, mercapto compounds and metal salts thereof described in No. 36, JP-A-Sho-tko-r7ri! Acetylene compounds such as those described in 7 can be used.

As the reducing agent used in the photosensitive material of the present invention, known reducing agents can be used. Further, a dye-donating compound having reducing properties, which will be described later, is also included (in this case, other reducing agents can also be used in combination).

Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.

Examples of reducing agents used in the photosensitive material of the present invention include No. V-! of U.S. Pat. Column 0, Column 30-31 of Kou 113.21, Column 1/,
, No. 330,617, No. p, t 0,752, JP-A No. 1sO-/≠033! No. (17) to (/l) pages,
same! 7-San〇kohiro! No. J-4-13!1736,
Same Tatar/71 Hiro! No. 1? -! 3113/issue, same! ? -/r24A'l issue, same ry-tr, 2uro issue, same JO-//ri issue 515, same 60-/kot μst issue, same to-/2r4A3 issue, same to-iyrza
No. o, same tO-/I/7 Dako No., same j/-, Zjri 21
No. 7, t2-24A4AOII No. 41, A,, 2
-/ From the 37.2/3 issue, the same tco/J/co! There are reducing agents and reducing agent precursors described in European Patent No. 0, 7, No. 6A, pages 7-1.

US time ifF'! ! Combinations of various reducing agents can also be used, such as those disclosed in No. iii, oiy, rty.

When using a diffusion-resistant reducing agent, an electron transfer agent may be added as necessary to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. can be used in combination with an electron transfer agent precursor.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or precursors thereof.

It is desirable that the mobility of the electron transfer agent f or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are l-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive element, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-Sho J-3-/10r27, and dye-donating compounds with diffusion resistance and reducing properties described below.

In the present invention, the addition of the reducing agent is o per 7 moles of silver.
, oi-2o mol, particularly preferably O0/-10 mol.

In the light-sensitive material of the present invention, silver can be used as an image-forming substance. It may also contain compounds that produce or release dyes, ie, dye-donating compounds.

Examples of dye-providing compounds that can be used in the photographic material of the present invention include compounds (couplers) that form dyes through oxidative coupling reactions. This turnip 2- may be a reference coupler or a lambda equivalent coupler. Also preferred are coequivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction.

This diffusion-resistant group may form a polymer chain.

Specific examples of color developers and couplers can be found in James, “
The Theory Op the 7 Autograph Process JJ4' version (T, H, James-TheTheor
y of the PhotographicP
rocess”) Kota l~33hiro pages, and 3!≠~3
6/page, JP-A-Sho II-/λ3! No. 33, same jj-/Mairi O-san No. 6, same! I-/+riO≠No. 7, Miyayoter////
The 3rd issue, the same 5 tar/24A3 Tata issue, the same! ter17≠r
IG issue, same J Turco 3/J 3 issue, same! ? -23/! No. 0, No. 40-2? No. 10, To--ta! No. 7, No. 6
0-/g24Aλ, 60-λJ$74<, 4O
- It is described in detail in the Jjλ issue, etc.

Further, as another example of the dye-providing compound, there can be mentioned a compound having a function of releasing or diffusing a diffusible dye in an imagewise manner. Compounds of this type can be represented by the following general formula (LIJ).

(Dye −Y)n Z (L I
JDye represents a dye group, a numerically shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z corresponds to or inversely corresponds to a photosensitive silver salt with an imagewise latent image. Correspondingly, a difference is created in the diffusivity of the compound represented by (Dye -Y)n-Z, or Dye is released and the released Dye and (Dye -Y)1-Z are combined. represents a group having properties that cause a difference in diffusivity between the groups, n represents/or C, and when n is C,
ye-Y may be the same or different.

Specific examples of the dye-providing compound represented by the general formula (Ll) include the following compounds (1) to (2).

Note that ■ to ■ below are those that form a diffusive dye image (positive dye image) in reverse response to silver halide development.
(2) and (2) form a diffusive dye image (negative dye image) in response to silver halide development.

■U.S. Patent No. 3. /31t, 76≠ issue, same number 3゜3tλ
, t72, same no. 3. Jri 7.400, same No. J, j4
vinegar,! ≠No. 5, No. 31≠8'2. A dye developer in which a hydroquinone developer and a dye component are linked, as described in No. 7, etc. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

■U.S. Patent No. 44,103. /! As described in No. 7, etc., non-diffusible compounds that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide can also be used. An example is U.S. Patent No. 3. Ri1
A compound that releases a diffusible dye by an intramolecular nucleophilic @pincer reaction described in No. 0,177, etc., US% Liver No. 4<,/Wata. Compounds that release an eri-diffusible dye in response to the intramolecular winding reaction of the inoxacilone ring, which are described in Reference 3 and the like, can be mentioned.

■As stated in U.S. Patent No. 3, sty, λri No. 0, European Patent No. λko 0,7≠4Ako, Publication Branch Axis 17-A/Tata, etc., it remained unoxidized by development. Non-diffusible compounds that react with reducing agents to release diffusible dyes can also be used.

Examples include U.S. Tokkin No. 3, i3li, it2, ag4t, li9. i7W issue, Tokukai Shozy-/r! 33
No. 3, same! Compounds that release diffusible dyes by intramolecular nucleophilic substitution reaction after being reduced, as described in US Pat. No. 7-1111713, etc.;
Tokukai Akira! Compounds that release eli-diffusible dyes due to intramolecular electron transfer reactions after being reduced, described in 10Ittty No. 10, No. 1#2j7, RD21102j (/PI Hirotoshi), etc., Nishi Unique IFF No. i, oor, zrrh
No., Japanese Patent Application Publication No. 2130, U.S. Patent No. 3
Compounds whose single bonds are cleaved after reduction to release a diffusible dye, which are described in No. 4c3, 193, No. a, tip, rrtt, etc.; A nitro compound that releases a diffusible dye after accepting electrons, which has been proposed in the US Special Proposal No. ≠.

Examples include compounds that release a diffusible dye after accepting electrons, as described in No. 10, No. 10, etc.

In addition, as a preferable item, European special liver No. 220.7
1/Ltk2 issue, public branch axis 17-J/Tata, special request Shoj,
Compounds having an N-X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in 2-3 Geta J No. 3, the same as 1-3≠RIj Hiro No., etc. , special application 1986-
802-X (
xi A compound having the same a) as above and an electron-withdrawing group, po-x in one molecule described in Japanese Patent Application No.
A compound having a bond (X has the same meaning as above) and an electron-withdrawing group, a c-x' bond (synonymous with X'UX or -S O2- Compounds having an electron-withdrawing group and an electron-withdrawing group are mentioned.

Among these, compounds having an N-X bond and an electron-withdrawing group in the molecule are particularly preferred. Specific examples thereof include compounds (1) to (3) described in European Patent No. 0,7,
(7) to (10), (lλ), (/3).

(/!), (23) ~ (2t), (31), (32),
(3j), (3a), (4tO), (gl), (≠Hiroshi), (!3) ~ (evening?), (tda), (70), public branch axis 17-619? and compounds (ii) to (23).

■A compound that is a coupler that has a diffusible dye as a leaving group and releases the diffusible dye upon reaction with the oxidized form of a reducing agent (D
DR coupler]. Specifically, British Patent No. 1,330.
! -2 Hiro No., Special Publication No. 4CR-32,111, U.S. Patent Department 1.4AIIl, ? 4cO No. 11, 1I74t
, No. 167, No. p, 4Ari, pH No., etc.

■Reducing to silver halide or organic silver salt,
A compound that releases a diffusible dye upon reduction of its partner (DD
R compound). Since this compound does not require the use of any other reducing agent, it is preferable since there is no problem of image staining due to oxidative decomposition products of the reducing agent.

A typical example is US Patent Department 3. ri 21,3t, 44,0!3,3t, ≠, oss, u2,
Same No.μ,! 3t, No. 122, JP-A No. JP-4PrJt, No. 3-3119, JP-A-J/
-104c, No. 3443, RD17≠t! No. 3,721. It-No. 3.7, No. 113,
Same No. 3, 1, P3 issue, JP-A-5R-II,! 37
No. 7-/7r4co, U.S. Patent Division 44. J-
No. 00,626, etc. Specific examples of DRR compounds include the compounds described in the above-mentioned U.S. Pat. (/l~
(3), (io) ~ (13), (16) ~ (19), (
kot) ~ (30), (ii)-gz), (3t) ~ (p
O), (4(J) to (6hiro)) are preferred. Also, see U.S. Pat.

Also useful are the compounds described in columns 37 to 3 of No. 632, ≠or.

In addition, as a dye-donating compound other than the above-mentioned couplers and the general formula (LIJ), dye silver compounds in which an organic silver salt and a dye are combined (Research Disclosure Magazine 17t
Azo dyes used in silver dye bleaching methods (U.S. Patent Department 'A, 21!, RI! 7, Research Disclosure magazine, RI 7, etc.) No. 30-32), leuco dyes (U.S. Patent No. 3.?r
j,! tj, ≠, 0.2, t/7, etc.) can also be used.

Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents are US patented! It can be introduced into the layer of the photosensitive element by known methods such as the method described in @λ, 3 Coco, No. 027. In this case, Tokukai Akira! Y-riiztt issue, same 1
? -/71rlljI issue, samejP-/7r4AJ- issue,
Same as '? -/No. 711713, same 1? -/7r! J1, same 1? -/7r! J11, same! Tar 171μ! If necessary, use high boiling point organic solvents such as those described in No. 7! Used in combination with a low boiling point organic solvent of 0°C to /100°C,
Can be used.

The amount of high boiling point organic solvent is the dye-providing compound used/9
IO9 or less, preferably! It is less than or equal to y. Also, the binder tg should be less than /eQ, and even 0. rQ
C or less, especially o, 3cc or less is suitable.

Special public Akira number l-32113, Special public Akira! /-j5'riμ3
The dispersion method using polymers described in No.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, Tokukai Akira! Those listed as surfactants on pages (37) to (31) of No. Tar/j7AjA can be used.

In the light-sensitive material of the present invention, a compound can be used that activates development and simultaneously stabilizes the image. Preferred structural compounds are described in U.S. Pat.
o, t26 No. 51-! It is listed in the column.

A hydrophilic binder is preferably used for the photosensitive material. An example of this is JP-A-Sho t2-ko! 31! ? Examples include those described on pages (colo) to (-r) of the issue. Specifically, transparent or translucent hydrophilic binders are preferred, such as gelatin, tannins such as gelatin fermentation conductors, cellulose derivatives, starch, gum arabic, etc.
Examples include natural compounds such as polysaccharides such as dextran and pullulan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. In addition, the super absorbent polymer described in JP-A-4.2-217!260 etc., namely -COOM or -8
Oa M (M is a hydrogen atom or alkali gold IA) t'
A homopolymer of vinyl monomers having the same or a copolymer of these vinyl monomers with each other or with other vinyl monomers (
For example, methacrylic v! Sodium, ammonium methacrylate, Sumikagel L-jl ()% manufactured by Sumitomo Chemical ■ were used.

Two or more of these binders can also be used in combination.

When using a system that performs development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water.

Further, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the C dye from being retransferred from the dye fixing element to another object after transfer.

In the present invention, the binder application t is 2 per m2.
The weight is preferably 09 or less, particularly 109 or less, and more preferably 7g or less.

Hardeners used in photosensitive materials include US Pat.
No. 1,732, column 11, Tokukai Sho! Tar 1ittzz,
Examples include hardeners described in 6 Koko Hirojλ≦1, 4/-/IF Hiro 2, and the like.

More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, etc.) vinylsulfone hardeners (IN, N'-ethylene-bis(vinylsulfonylacetamide) ) ethane etc.),
Examples include h-methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in %Kaisho tλ-23≠117, etc.).

Various development stoppers can be used in the photosensitive material of the present invention, particularly in the heat-developable photosensitive material, in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base or reacts with the base to lower the base level in the film and stop the development after proper development, or a compound that interacts with the silver salt. A compound that inhibits development.

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a base that coexists with heating, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors.

For more details, please visit Tokukai Sho t Coco! 3/! I; Ri issue (3/)
It is described on pages ~(3).

The constituent layers (including the back layer) of the photosensitive material of the present invention include dimensional stabilization, curl prevention, adhesion prevention, film crack prevention,
For the purpose of improving membrane properties such as preventing pressure increase/decrease, etc., 6C containing various polymer latexes can be made. in particular,
Time opening l] 8t Koko Hiro! λ! r, 4j-/3ttu
Any of the polymer latexes described in No. R, No. 62-/10ois 6, etc. can be used.

In the light-sensitive material of the present invention, a high-boiling organic solvent can be used as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive element and the dye-fixing element. In terms of structure, it is JP-A-Sho t2-2.
There are those described in Yo 31! No. 2, page (λ!), No. 62-2441213, etc.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethyl silicone oil to modified silicone oils in which various organic groups are introduced into dimethyl cloxane. For example,
Various modified silicone oils listed in the "Modified Silicone Oil" technical data Pj-/FB published by Shin-Etsu Silicone,
Especially carboxy-modified silicone (PJ product name-Coco-3)
710) etc. are effective.

Also, JP-A-62-2/1?13, % patent application No. 62-234
The silicone oil described in No. 17 is also effective.

An anti-fading agent may be used in the light-sensitive material of the present invention. Antifading agents include, for example, antioxidants, UV absorbers, or certain metal complexes.

Examples of antioxidants include chroman thread compounds, coumaran thread compounds, phenolic compounds (e.g. hindered phenols), hydroquinone derivatives, hindered amine cast conductors, and spiroindane compounds. Compounds described in Hirohiro No. 6 are also effective.

Benzotriazole compounds (
American watch No. 1. ! 33.7?4A, etc., thiacylidone compounds (US Clock No. 3.3! Colo 1/etc.)
, benzophenone compounds (JP-A Akihiro t-Core j reference etc.), other JP-A Akihiro t-Core j reference No. 1111, JP-A No. 1111, Akihiro tλ-1
There are compounds described in stt da No. 1, stt da No. 6/-rr Jjj, etc. Also, JP-A-62-. The ultraviolet absorbing polymer described in No. 240112 is also effective.

As metal complexes, U.S. Pat. !
No., Hiromu, 24cj, No. 0IIr, columns 3-36, No.≠, Kojμ, /91 No. 3~! Column, JP-A-ShojO-474
Hiroshi No. 6λ-/71N1, No. J/-112! There are compounds described in Japanese Patent Application No. J7J to (if), Japanese Patent Application No. 103, Japanese Patent Application No. 62-23, No. 310-6, Japanese Patent Application No. 62-430!26, etc.

An example of a useful anti-fading agent is JP-A No. 621/1272 (
/Jri) to (/J7) pages.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

The photosensitive material VC of the present invention may contain a fluorescent brightener. A fluorescent brightener treatment solution or the like can also be supplied from outside. An example is K, Veenkataraman@
l'-The Chemistry of 5y
ntheticDye sj Volume V Chapter, Tokukai Sho t/
-/4c37! Compounds listed in No. 1, etc. can be mentioned. Examples of the erythropoietic compounds include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, caftalimide compounds, pyrazoline compounds, and carbosteryl compounds.

Fluorescent brighteners can be used in combination with antifade agents.

Various surfactants can be used in the photosensitive material of the present invention for the purposes of coating aids, improving peelability, improving slipperiness, preventing static electricity, promoting development, and the like. Specific examples of surfactants are described in JP-A No. 77-47, JP-A-42-1!34417, and the like.

The photosensitive material of the present invention may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static electricity, improving peelability, and the like. Typical example of organic fluoro compound
90!3 No. r-/7@, JP-A-61-Koori Hirohiro No.,
62-iizt, tt, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. can be mentioned.

A matting agent can be used in the photosensitive material of the present invention.

As a matting agent, silicon dioxide, polyolefin or polymethacrylate, etc., are used.
In addition to the compounds described on page 1, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
There is a compound described in No. z.

In addition, the photosensitive material of the present invention may contain a thermal solvent, an antifoaming agent, an antibacterial and anti-spill agent, colloidal silica, and the like. Examples of media for these additives are described in Japanese Patent Application Laid-open No. 4/1989-r r J s on pages (26) to (3-2).

Examples of the support for the photosensitive material of the present invention include paper, synthetic polymers (
film). Media include polyethylene terephthalate, polycarbinate, polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose (for example, triacetyl cellulose), or films containing pigments such as titanium oxide.
In addition, film-process synthetic paper made from polypropylene etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, Baryta paper, Coachia paper (especially cast coated paper), metal, cloth. glass, etc. are used.

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition to this, '3/! No. (2F) ~ (
The supports described on page 3/) can be used.

A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

Methods for exposing and writing images on the photosensitive material of the present invention include, for example, directly photographing landscapes or people using a camera, exposing through reversal film or negative film using a printer or enlarger, etc. A method of scanning and exposing an original image through a slit using an exposure device of a copying machine, a method of transmitting image information via an electric signal, a method of emitting light from a diode, various lasers, etc., a method of transmitting image information to a CRT, liquid crystal display, etc. There is a method of outputting the image to an image display device such as an electroluminescence display or a plasma display and exposing it directly or via an optical system.

Light sources for recording images on photosensitive materials include, as mentioned above, natural light, tungsten lamps, light emitting diodes, laser light sources, CRT sources, etc., as disclosed in US Patent No. V, ZO0,4.
The light sources listed in column j6 can be used.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (INTSC), and images obtained by dividing an original picture into a large number of pixels using a scanner. signal, CG,
Image signals created using a computer such as CAD can be used.

When the photosensitive material of the present invention is used for heat development, the heating temperature in the heat development process is approximately ! It can be developed at a temperature of 0°C to about 2J00C, but a temperature of about 0C to about /100C is particularly useful.

In the case of a dye diffusion transfer type heat-developable photosensitive material, the dye diffusion transfer step may be performed simultaneously with the heat development or after the heat development step is completed. In the latter case, the heating temperature in the transfer step can be within a temperature range from the temperature in the heat development step, but is particularly preferably at a temperature of zo0c or higher and about 1o0c lower than the temperature in the heat development step.

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Mata, Japanese Patent Application Publication No. 1977-2/lll-1Ij, same t/
- A small amount of solvent (
Also useful is a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of water (particularly water). In this method, the heating temperature is preferably above to'C and below the boiling point of the solvent, for example when the solvent is water! It is desirable that it is not less than o'c and not more than 1oo0c.

Examples of solvents used to accelerate development/transfer of the diffusible dye to the dye fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base. . In addition, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be conveniently used. In addition, surfactants, antifoggants,
A complex-forming compound etc. may also be included in the solvent.

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, or both.

The amount used is less than the weight of the solvent corresponding to the maximum swelling volume of the entire coated film (in particular, a small quantity of 2, which is calculated by subtracting the 'M amount of the total coated film from the M amount of the solvent corresponding to the maximum swelling volume of the entire coated film). So it's 1.

As a method for applying a solvent to the photosensitive layer or the dye-fixing layer, there is, for example, the method described in Japanese Patent Application Laid-Open No. 1997-110007 (26). It is also possible to use the solvent by preliminarily incorporating it into the photosensitive element, the dye fixing element, or both, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperatures is incorporated into the light-sensitive material or dye fixing material.

The layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or its adjacent layer.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.

Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or Matsumoto process include contact with a heated block or plate, a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far-infrared lamp heater, etc. or passing through a high-temperature atmosphere. Also,
A resistive heating layer may be provided on the photosensitive material or the dye-fixing material and heated by applying electricity to the layer. As a heating element layer, JP-A-6/-/uJ-! Those described in No. 4cf etc. can be used.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in JP-A-Kokai Shoj/-/≠7.
The method described on page 2μHiro issue (λ7) can be applied.

Both F'X and 'Fji thermal development apparatuses can be used to process the photosensitive material of the present invention. For example, Tokukai Akira! Turf j, 2≠7, same turf 7775 hiro 7, turf j ter/1
Apparatuses such as those described in No. 13j3, No. 40-/191/, Hirohiro Utility Model Publication No. 6.2-Coj9, etc. are preferably used.

When the photographic material of the present invention is a dye-forming type, the (thermal) development step can be followed by a desilvering step, a water washing step, and a drying step, if necessary.

Example 1 A color photosensitive material ioi having a multilayer structure as shown in Table 1 was prepared.

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4g to! y How to make emulsion (I) for the first layer will be described.

A well-stirred gelatin aqueous solution (containing 201 gelatin and 3 g of sodium chloride in water/000d, 7j'C
An aqueous solution containing sodium chloride and potassium bromide (kept warm at
silver nitrate (o, r) dissolved in d) was simultaneously μ
ff57101 at equal flow rate for O minutes. Ta. In this way, the average particle size is 0°3! A monodisperse cubic silver chlorobromide emulsion (bromine rOmolti) of μ was prepared.

After washing with water and desalting, thiosulfate tRf thorium j■ and Hiro-Hydrokiku-6-Tateru/. 3. Chemical sensitization was carried out with TOOC by adding 38.7-chitrazaindenko Oda. Emulsion yield was toog.

Next, we will discuss how to prepare the emulsion (n) for the third layer.

A well-stirred gelatin aqueous solution (water ioo.

Contains gelatinko OI and sodium chloride 3fNt in d7
An aqueous solution containing sodium chloride and potassium bromide (kept warm at J'C), an aqueous silver nitrate solution (0.2 tamol of silver nitrate dissolved in water too), and the following dye solution (1). were simultaneously added at equal flow rates over +0 minutes. In this way, the average particle size is 0.3!
A monodisperse cubic silver chlorobromide emulsion (10 mol % of bromine) on which a μ dye was adsorbed was prepared.

After washing with water and desalting, thorium thiosulfate and Hiroshi-hydroxy-t-methyl-/, 3.3a, 7-thitrazaindene 2
Chemical sensitization was performed at 0c to 0c. Emulsion yield was toog.

Dye solution [(1)... A sensitizing dye ito~ having the following structure dissolved in methanol≠oottt [Next, the method for preparing the emulsion (Ill) for the j-th pigeon will be described.

A well-stirred aqueous gelatin solution (gelatin Oy and ammonium dissolved in water 10001 and kept warm in a zooc), an aqueous solution 10100O containing potassium iodide and potassium bromide, and a silver nitrate aqueous solution (10100O
1 mole of silver nitrate dissolved in the solution) was added at the same time while keeping the pAg constant. In this way, the average particle size is 0. j μ monodisperse octahedral silver iodobromide emulsion (iodine j mol%)
1! : Prepared.

After washing with water and desalting, chloroauric acid (lIL hydrate)! Gold and sulfur sensitization was performed at 60°C by adding 2 g of sodium thiosulfate. The yield of the emulsion was thzKP.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

Yellow dye-donating substance (1)/39, high boiling point organic solvent (4)"6, r9. Electron donor (1)"4(,
4! g, added and dissolved in cyclohexano 7371111,
IO% gelatin solution/00fl and sodium dodecylbenzenesulfonate,! After stirring and mixing with 60 ml of aqueous solution of
It was dispersed. This dispersion is called a yellow dye-providing substance dispersion.

Magenta dye-donor substance (2)'/l, rg, high boiling point organic solvent (1)'r,≠y, child donor (1)3≠,j
P, was added and dissolved in 37 ml of cyclohexanone, and io%
2. Gelatin solution ioog, sodium dodecylbenzenesulfonate. After stirring and mixing 60 g of the Yochi aqueous solution, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion is called a dispersion of a magenta dye-providing substance.

Cyan dye-donating substance (z), 4 g, high boiling point organic solvent (1) 7.7, 9.
Add and dissolve cyclohexanone J7dVc, 70% gelatin solution 1009 and sodium dodecylbenzenesulfonate. ! After stirring and mixing the mixture with the aqueous solution TOAT, the mixture was dispersed using a homogenizer at 10OORPM for LO separation. This dispersion is called a dispersion of a cyan dye-providing substance.

Next, we will discuss how to make the dye fixing material.

A dye fixing material R-/ was prepared by coating on a paper support laminated with polyethylene according to the composition shown in the following table.

Table 2 Composition of dye fixing material R-/ Table 2 Composition of dye fixing material R-/ (continued) Silicone oil "I CH3CHa (CH2) a C00L-i
Cti3 surfactant 412 aerosol OT reagent
Cs F s 7 So 2NCH2C00KC3”
7 Tatami 4 ■ H3 Holimer 5 Vinyl alcohol sodium acrylate copolymer (7!/co! molar ratio) Tatami 7 Dextran (molecular weight 70,000) Mordant 6 S02 8 High boiling point organic solvent Leofostaj (manufactured by Ajinomoto ■) ) Hardener “9 (C)12) (-0-C)12-CI-i-CM±
2 Matting agent "10 benzoguanamine resin average particle size ioμ Photosensitive material 10/ is placed in a stainless steel container and sealed as it is, sample ■. Silica gel is placed in a stainless steel container and sealed, sample ■, made of stainless steel. Sample ■ is a container in which a mixture of hydroquinone, sodium sulfite, and sodium carbonate (lit ratio / : / : 2) is placed and sealed. In addition, the inside of a stainless steel container is filled with nitrogen gas and then sealed. Sample ① was prepared by placing silica gel in a container, and sample V was obtained by replacing the container with nitrogen gas.

Immediately after producing photosensitive material 10/, and after storing samples 1 to V for one month under the temperature condition of μQ0C, using a tungsten light bulb, B, G, and R whose concentrations were continuously changing were examined.
and exposed for 0 seconds at zooolux through gray color separation filters.

While feeding this exposed light-sensitive material at a linear speed of 20 mm/sec, 7 m2 of water was supplied to the emulsion surface using a wire bar, and then immediately overlaid with dye fixing material R-/ so that the film surface was in contact with the emulsion surface.

Using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was rz'c, it was immediately heated for -0 seconds. Next, when peeled off from the dye fixing material, 81G, R
Clear images of blue, green, red, and gray were obtained in response to color separation filters for color separation and gray.

Table 3 shows the results of measuring the maximum density (DmaxJ) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part.

Example 2 The color photosensitive material 10 prepared in Example 1 was stored under the following conditions at a temperature of 0C for several months, and then processed in the same manner as in Example 1.

Sample 1: Enclose the photosensitive material in a polyethylene bag and store it protected from light.

Sample■ Mixture of ferrous sulfate and iron powder (weight ratio: 1/2)
Wrapped in paper and sealed in a polyethylene bag with photosensitive material, protected from light and stored.

Sample ■ Wrap silica gel in paper, seal it in a polyethylene bag with photosensitive material, and store it protected from light.

Sample ■ A mixture of ferrous sulfate, iron powder, and silica gel (weight ratio: 0.05% by weight) was wrapped in paper and sealed in a polyethylene bag along with the photosensitive material, and stored protected from light.

Sample ■ Light-sensitive material.Laminated with polyethylene while deaerating, and stored protected from light. Grey, some cyan, magenta,
The table shows the results of measuring Dmax and Dmin of each color of yellow.

Example 3 Table! A color photosensitive material ZOI having a multilayer structure shown in FIG.

Except for those described below, those described in Photosensitive Material 10/ of Example 1 were used.

Reducing agent (1) "Dye-donating substance yellow (7)""Cyan(li)" Immediately after preparing the photosensitive material 30/ and after storing it for one evening at 1IO0C under the conditions of samples 1 to ① shown in Example 2. B and G using tungsten bulbs with continuous @degree changes
1 at 1000 lux through a %R three-color separation filter
Exposure for seconds.

Omg/m2 on the emulsion side of this exposed light-sensitive material
of water was supplied with a wire bar, and the dye fixing material R-/ of Example 1 was layered so that the film surface was in contact with the dye fixing material R-/. It was heated to 0C for 15 seconds on a heat block. The result B
, G, R corresponding to the exposure (20-, magenta,
A clear negative cyan image was obtained.

At this time, Dmax of 0+, magenta, and cyan
, Dmin are shown in Table 6.

Example 4 A color photosensitive material '70/ having a multilayer structure shown in Table 7 was prepared.

The materials described in Example 3, Photosensitive Material 30/, were used except for those described below.

Surfactant (j)” Reducing agent (,2)” Sensitizing dye (2) + <J> 4k (≠)” (yo)” Nucleating agent (1)” Cyan dye donating compound (≠)” 01+ oc16 'i33 Magenta dye-providing compound (, 1)'' Yea-Dye-providing compound (6) ``Development regulator precursor (1)'' Preparation of internal latent image type emulsion MV) An aqueous solution of potassium bromide and an aqueous solution of silver nitrate @ They were simultaneously added to a diluted gelatin aqueous solution over 20 minutes at 7J0C with vigorous stirring to obtain an octahedral monodisperse silver bromide emulsion with an average grain size of 0 μμm.

Add to this emulsion t of sodium thiosulfate (! hydrate) and chlorauric acid (! hydrate) per mole of silver,
Chemical sensitization treatment was performed by heating at lt'c for 10 minutes. Using the thus obtained silver bromide particles as a core, potassium bromide and silver nitrate were further added for 4 AO minutes in the same precipitation environment as when forming the core particles to finally form octahedral monodisperse cores with an average particle diameter of 0.7 μm. /shell silver bromide emulsion was obtained.

After washing with water and desalting, sodium thiosulfate and chloroauric acid (Kosui salt) were added to this emulsion in an amount of 1.0% per mole of silver, and chemical sensitization was carried out by heating at tOoC for 60 minutes. A developing emulsion was obtained.

Preparation of internal latent image emulsion (V): Add an aqueous solution of potassium bromide and an aqueous solution of silver nitrate to an aqueous gelatin solution containing potassium bromide (30 g of gelatin in 700 ml of water).
(containing 6 g of potassium bromide) with vigorous stirring at 7z'c for 10 minutes to obtain a silver bromide emulsion. The pAg during addition was kept at r, r.

Before precipitation (before simultaneous mixing), a silver halide solvent of 119 g/mole of silver was added to the aqueous gelatin solution.

When the precipitation was completed, octahedral silver bromide crystals with a uniform grain size and an average grain size of 0.1 μm were produced.

The silver bromide particles were then treated with sodium lithiosulfate per mole of silver, rm9 (! hydrate), and 2.5 g of chloroauric acid (μ hydrate). Chemical sensitization treatment was carried out by adding IIt■ and heating at 7!0C for too long. The core silver bromide emulsion chemically sensitized in this way has the same p.p.
An aqueous solution of potassium bromide and silver nitrate was mixed and added simultaneously over 4 At minutes to precipitate a core/shell emulsion, and hydrogen peroxide was added as an oxidizing agent per mole of silver at 7!0C. After heating for t minutes, the mixture was washed with water to obtain an octahedral silver bromide emulsion with an average grain size of 1 μm.

Next, to this internal latent image type core/shell silver bromide emulsion, sodium lithiosulfate (!
The particles were heated at oC for up to minutes to chemically sensitize the particle surface.

In addition, the concentration of the silver aqueous solution used in the preparation of the core/shell emulsion was 03/i, 2zl to 7 mol Ag in both the core and shell parts.
To form particles in the core part, 0, it mol of silver was added, and to form a shell part, 0.3 μm mol of silver was added.

The concentration of the potassium bromide aqueous solution was 7 mol KBr/II in both the core and shell parts.

Immediately after the photosensitive material No. 07 was prepared and after being stored at 0°C for 7 months under the conditions of Samples ■ to V shown in Example 2, using a tungsten light bulb, B, whose concentration was continuously changing,
CoOOO through G, R and gray color separation filters
Exposure was made for 1710 seconds at lux.

20 m1/m2 of water was supplied to the emulsion surface of this exposed light-sensitive material, and immediately thereafter, the material was superimposed so that the film surface was in contact with the dye fixing material. The dye fixing materials are shown in Table 2 of Example 1.
Guanidine picolinate in the second layer of R-/ shown in 2.2
Dye fixing material R-2 having the same structure as R-/ was used except that the concentration was changed to 0 g/m2.

The film was heated for 25 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was zo 0C. Both materials were then peeled off and clear images of blue, green, red and gray were obtained on the dye-fixing material using B, 0% R and gray color separation filters.

Dma for some cyan, magenta, and yellow colors
The results of measuring x and Dmin are shown in Table r.

From the above examples, it was found that all of Samples 1 to 2, which were stored in the presence of a desiccant and/or an antioxidant, had excellent stability during storage of the photosensitive materials.

Claims (1)

[Claims] A silver halide photosensitive material comprising a silver halide photosensitive material containing at least a slightly water-soluble basic metal compound and a reducing agent on a support and stored in the presence of a desiccant and/or an antioxidant. How to save.