JPS6238460A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain a sharp image having a small fogging density in a snort period by heating a photosensitive material in the presence of water, base and/or base precursor and antifogging agent after or simultaneously with imagewise exposure and forming an imagewise distribution of movable dyes. CONSTITUTION:The photosensitive material contg. at least photosensitive silver halide, binder and dye donative material on a base is heated in the presence of the water, the base and/or base precursor and at least one of the antifogging agent after or simultaneously with imagewise exposure to form the imagewise distribution of the movable dyes. The antifogging agent to be used is simply required to exist in the stage of heating and is not always required to be preliminarily made to exist in the photosensitive material. The fluctuation of the photographic characteristics is resulted upon aging of the photosensitive material and the prepn. of the stable photosensitive material is difficult if a large amt. of the antifogging agent is preliminarily incorporated into the photosensitive material. The method consisting not in preliminarily incorporating the antifogging agent into the photosensitive material but is supplying the same from the outside in the stage of heating is effective to stably obtain the image.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for forming a dye image by heating, and in particular to a method for preventing fog during development and for obtaining an image that is stable against fluctuations in development conditions. Regarding the method.

(Prior art) Photography using silver halide has been the most widely used method since it has excellent photographic properties such as sensitivity and gradation circle compared to other photographic methods such as electrophotography and diazo photography. I've been exposed to it. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developer, etc. to the dry processing using heating, etc. has been developed.

Heat-developable photosensitive materials are well known in the art, and for information on heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979), pages 553 and 555;
Published in April 1978, 40 pages of video information, [Nebletts, Handbook of Photography and Professionals] 7th edition (Nebletts, Handbook of Photography)
Photography and Reprograph
y 7th Ed, ) Van Nostrandtreinhold 1 Company (Van No5traod
Reinhold Company), pages 32-33, U.S. Patent No. 3.152904, No. 3301.678
No. 3.392020, No. 3.457.075,
British Patent No. L131,108, No. 1,167;777
No. and Research Disclosure g 1978 6
It is described in the monthly issue 9-15 Easy (f (D-17029)).

Further, various methods of obtaining color images by heating are described, for example, in Research Disclosure Magazine, May 1978 issue, 54-58.
-! - Ji (RD-16966) April 1976 issue 3
0-32E:) (RD-14433), U.S. Pat.
, No. 867, No. 447 & 927, No. 4507.380
No. 4,50Q626, No. 4,484914, etc. All of these methods generate or release dyes by heating to form an image-like distribution of the dye, and are characterized by the ability to obtain an image-like distribution of the dye in a short period of time.

(Problems to be Solved by the Invention) However, when trying to obtain a high dye density by heating, fog density also increases, making it difficult to obtain a sharp image.

Therefore, methods of incorporating various antifoggants into photosensitive materials have been proposed; for example, British Patent No. 2135.465,
It is described in US Pat. No. 450Q627 and the like. However, when it is included in a 4Q photosensitive material, it tends to cause a decrease in sensitivity and development speed, making it difficult to use a stable photosensitive material.
) is not easy.

Further, the above-described image forming method usually requires a step of forming an image-like mobile dye by heating and a step of transferring this dye to a dye fixing layer. If these steps can be performed simultaneously, the processing can be speeded up and simplified.

Therefore, the object of the present invention is, firstly, to provide a new method for forming the dye side 18 by heating, and to overcome all the drawbacks of the hitherto known photosensitive materials.

A second object of the present invention is to provide a method for obtaining clear images with low fog density in a short time.

A third object of the present invention is to provide an i-O method for obtaining images that are stable against fluctuations in heating temperature.

A fourth object of the present invention is to provide a method for obtaining images that are stable against variations in heating time.

A fifth object of the present invention is to provide a method for obtaining stable images using a simple method.

(Structure of the Invention) The object of the present invention is to apply water, a base, and/or This is accomplished by an imaging process that involves heating in the presence of a base precursor and at least one antifoggant to form an imagewise distribution of mobile dye.

In the present invention, the light-sensitive material is heated in the presence of water, a base and/or a base precursor, and an antifoggant after or simultaneously with imagewise exposure to form an imagewise distribution of mobile dyes. The antifoggant used in the present invention only needs to be present during heating, and does not necessarily need to be present in the photosensitive material in advance. Pre-containing a large amount of antifoggant in a photosensitive material causes fluctuations in the photographic properties of the photosensitive material over time, making it difficult to produce a stable photosensitive material. Therefore, it is effective to supply the antifoggant externally during heating, rather than including it in the photosensitive material in advance, in order to stably obtain images.

In the present invention, it is preferable to include the antifoggant in water supplied from the outside and supply it to the light-sensitive material and/or the dye-fixing material. With this method, the antifoggant is applied immediately before heating, thereby eliminating the disadvantage of causing undesirable aging of the photosensitive material.

The antifoggants used in the present invention include compounds known in the photographic industry.

water-soluble zinc salts of Belgian Patent No. 663,269; oxides of basic metal salts of U.S. Pat. No. 1,975,199; Belgian Patent No. 4;
Inorganic compounds such as boron compounds of No. 725,078, Japanese Patent Publication No. 43-7570, Belgian Patent No. 677.337
No., mercury compounds of British Patent No. 1,067.066, U.S. Patent IC:lL 297.445, West German Patent No. 251
α464, halogen-containing compound described in Japanese Patent Publication No. 51-41056, U.S. Patent No. 3.22 & 770, U.S. Patent No. λ65
α760, Special Publication No. 43-13496, No. 43-10
256, phenol derivatives represented by phenol, gallic acid, catechol, achnophenol, etc. described in JP-A-54-83420, JP-A-47-8725, JP-A-4
No. 7-30206, No. 47-4417, No. 51-25
No. 340, JP-A No. 54-48735, JP-A No. 54-157
Alcohols such as pullulan, dextrin, thiosugar, and dihydroxy compounds of No. 31, US Patent No. L47
No. Z845, No. 3512982, French Patent No. 2.08
No. 4.347, No. 2084.348, British Patent No. L1
Acids such as polycarboxylic acids and nucleic acids and their derivatives, No. 65075, Japanese Patent Publication No. 39-22067, 39-220
No. 68, acetylene compounds of JP-A-54-99420, ketones of Ilgyi Patent No. 742,944, U.S. Pat.
No. 909.268, Special Publication No. 50-40665, No. 39
-2829, cations or itaine compounds of JP-A-55-29801, US Pat.
Nitro and nitroso compounds of No. 1.287.284,
U.S. Patent No. 3227.556, 390 (1321
No. 3655391, No. 391 Information 792, Belgian Patent No. 65Q938, British Patent No. 1 L 45469
No. 4, 1. OF+4805, JP-A-54-4852
No. 2 formazan, urethane, hydrazide 1, carbodiimide, ethyleneimine, azocarbonamide, guanadyl, amines such as amino acids, amides 5, azo and congeners, U.S. Patent Nos. A544,336 and 4001746
Phosphorus-containing compound of No. 381L896, U.S. Pat.
Llll, 697, Selenium-containing Compound, British Patent No. 1,
No. 344,525, No. 972211, L29 (18
No. 68, Special Publication No. 43-4136, No. 55-9696,
Compounds containing thione, sulfonyl, and sulfinyl groups, U.S. Pat. No. 314Q178, ibid. , 114,637
No. λ22Q839, No. 4.21 to 716, French Patent No. 2015.456, Belgian Patent No. 681,
No. 359, JP-A-54-14234, JP-A No. 55-533
No. 27, No. 54-158, 197, West German Patent Nos. 1 and 7
No. 97.027, No. 2921.817. Compounds having notothioether, disulfide, and mercapto groups, U.S. Patent No. 3137.578, &42 (1670),
No. 3759901, No. a62z340', No. 315
7.509, 3G No. 30.745, 326 (
i897, 3, 598.602, 20251
No. 2, JP-A-53-48723, JP-A No. 53-11682
No. 3, No. 55-5'L463, No. 55-79436, No. 50-104927, British Patent No. LO2L199
No. 91a061, No. 965,047, West German Patent No. 2501.261, L772424-1'j, P
JL No. 447.796, No. 2553127, Special Publication No. 49-8334, No. 49-10692, No. 53-2
No. 7933, No. 4fi-17513, French License No. 1
．． Heterocyclic compounds containing a hetero atom such as pyrazolidone, thiouracil, imidazole, triazole, tetrazole, pyrazole, inthiazole, thiadiazole, thiazoquinoline, etc. described in No. 351234, US Pat. No. 3,844,788 ,
Precursors described in Japanese Patent Publication No. 3535.115, Japanese Patent Publication No. 55-34927, Japanese Patent Publication No. 55-17369, Ilgi Patent No. 644382, British Patent No. 116 L264, British Patent No. 116 L24
No. 077, No. 1459160, No. L402819, U.S. Patent No. 1841878, No. 3,615.616
No., afi No. 71,255, JP-A-48-39039
No. 50-6323, Special Publication No. 48-34166J:
! Compounds described in F and the like can be used. Among the heterocyclic compounds containing heteroatoms, imidacillin conductor,
imidazole derivative, imidazole derivative, pyrazole/
conductor, pyrazole derivative, pyrazolone derivative, oxazoline conductor, oxazole wanderer, oxazolone derivative, thiazoline derivative, thiazole derivative, thiazolone derivative, selenazole derivative, selenazole derivative, selenazolone derivative, oxadiazole derivative, thiadiazole derivative, triazole derivative, tetrazole derivatives, benzimidazole derivatives, penztriazole derivatives, indazole derivatives, benzoxazole derivatives, inzthiazole derivatives, (fluoresenazole 184)
It is preferable that the compound be selected from pyrazine derivatives, pyrimidine derivatives, pyridazine derivatives, triazine derivatives, oxazine derivatives, thiazine derivatives, tetrazine derivatives, quinazoline derivatives, phthalazine derivatives, and polyazaindene derivatives.

In the present invention, it is preferable to use an antifoggant represented by the following general formula (I) or (n).

General formula (I) 7'-, NH . -1' In the above general formula (I), Z represents a group of nonmetallic atoms that together with the N atom form an imino-containing heterocycle.

General formula (II) -5-M The above general formula (■) (in which M represents hydrogen or alkali gold Ff4 atom, R is an aliphatic hydrocarbon group,
6 Representing an aromatic hydrocarbon group or a heterocyclic group In the present invention, among the cyclic imino compounds represented by the general formula (1), compounds represented by the following general formulas (2) to CJ) are preferred. Can be used.

General formula (11) General formula (IV) General formula (V) General formula (Vl) General formula (■) General formula (■) General formula (■) General formula (X) General formula (XI) General formula (Xll) In the above general formulas - (2), R, R2, R3 and R4 are each a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryl group, -NRR'
, -C:0O11't'', -CONFIFI/, -
N) IsO2Ft.

-8o t48Ft', -No□, halogen atom, -O
N or -OH (where B and R' each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and R
"represents an alkyl group, an aryl group, or an aralkyl group, and M represents a hydrogen atom or 4 alkali gold atoms).

When R□ and R2 are alkyl groups, they may be bonded to each other to form an aliphatic ring.

R5 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or -8
R/// (R″′ group is a hydrogen atom, an alkyl group,
Aryl group (f represents an alkyl group).

R6 is a water atom or an alkyl group, and R7 is a hydrogen atom, or an alkyl group or an aryl group.

F (8 represents argyl-water, aryl group, benzyl group, or pyridyl group) In the above, substituents for the heterocycle (F11 to F?
It is desirable that the total number of carbon atoms in 8) is 12 or less.

Furthermore, among the above, benzotriazole derivatives of the general formula (XII) are particularly preferred, while among the mercapto compounds represented by the general formula (■), compounds represented by the following general formula (Xllll) are preferred. Can be used.

General Formula (Xlll) In the above general formula (Xllll), Q is an oxygen atom, a sulfur atom, or a -NR'''' group (R'/// is a hydrogen atom,
(represents an alkyl group, an unsaturated alkyl group, or a substituted or unsubstituted aryl group or aralkyl group)
, Y and G are each a carbon atom or nitrogen atom, R□2 and R□3 are each a hydrogen atom, an alkyl group, an unsaturated alkyl group, a substituted or unsubstituted aryl group or an aralkyl group, -8R''''' or -NH2, where the R""' group is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkylcarboxylic acid or an alkali metal salt thereof, or an alkylsulfonic acid or an alkali metal salt thereof), Y and G When both are carbon atoms, R1□ may also form a substituted or unsubstituted aromatic carbocycle or nitrogen-containing heterocycle.

Among the compounds of general formula (Xlll), particularly preferred compounds are compounds represented by the following general formulas (XIV) and (XV).

(F114)m Here, m is an integer from O to 2, 4 represents the same group as Ro, and when m is 1 or 2a, the total number of carbon atoms is 112 or more.
is desirable.

Furthermore, in addition to the compounds represented by the general formulas CI) and (II), compounds represented by the following general formula

R-3-8□6 General formula (XVT) here”] 5
tR16 represents a substituted or unsubstituted aliphatic group, aryl group, or heterocyclic group, and R15-R16 may form a 5- to 7-membered ring together with S.

In the above general formula, the compounds represented by tn> or (XV) may be used alone or in combination. In particular, the general formula (IV
), (V), and (VI), rather than using them alone, the bencitol/azole derivatives of the general formula (■) or the general formula (X1ll'
) is extremely effective when used in combination with a nitrogen-containing heterocyclic compound having a mercapto group.

Typical specific examples of the compounds represented by the above general formulas (III) to (XV) are listed below, but the invention is not limited to the following compounds.

H e (Ill 1N □yen 8.)Fl C4H0 S S) I +631 )10(OH2)2S(C]-32)20
H (Foundation) HO(OH2)2S(CH2)2S(CH2
)20H(to)HO(CH2)3S(CH2)2S(C
;H2)30H+)J (HO(CH2)2S(CH
2k S6η Na03S(+;H2)3S(CH2)
2S(CH2)3So3Naf['a H(Xl'1
2(OH)C'H,,S(t;)(2)28G(2open(
OH)CH20Ht61 8000CI(2S(CH2
)28C:)(2COO)(σ(body H2NC:O(O
H2)2S (OH2)2S (CH2) 2COt4
H2q3C12H25-8-C12H25 σ4) C□8H37-8-C1□H25 In the present invention, the compounds of general formulas (1), (II), and (XVT) may be used in combination with other different antifoggants. good.

In the present invention, it is believed that the antifoggant is contained in the supplied water and diffuses into the photosensitive material in the presence of a base. Although the details of the mechanism are unknown, compounds with large molecular weights have a small effect, and compounds that are insoluble in basic aqueous solutions also have a small effect. Therefore, compounds that can be effectively used in the present invention have a molecular weight of 500 or less. It is preferable that the solubility in a specified solubility liquid is 0.014 or more.

The antifoggants of the present invention contain 5 x = 6 10 moles - 06 moles per 11 of water, preferably 5 x 10''5 to 0
．． It is effective to include 3 moles. In order to include the antifoggant in water, it may be simply dissolved in water, or it may be added after being dissolved in a base to be included as required. Furthermore, it may be added by emulsifying and dispersing it together with a high boiling point organic solvent by a known method used for dispersing hydrophobic photographic additives. Alternatively, it may be added after being dispersed using a colloid mill, a disperser using micro glass beads, or the like.

In the present invention, the antifoggant is used in a range of 0.001 to 100 mol of total silver in the light-sensitive material, particularly 0, O1 to 100 mol.
50 moles is preferable.

The base and/or base precursor used in the present invention may be contained in the above-mentioned water, and the photosensitive material and/or! Alternatively, it may be contained in a dye fixing material.

The bases of the present invention include hydroxides, carbonates, bicarbonates, borium salts, secondary and tertiary phosphorus salts of alkali metals, alkaline earth metals or quaternary alkylammoniums,
Inorganic bases such as quinolates and metaborates; organic bases such as aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and their carbonates; Bicarbonates, borates, secondary and tertiary phosphates, and the like.

Further, examples of the base precursor of the present invention include precursors of the aforementioned organic bases. The base precursor referred to herein is one that releases a basic component by heat or electrolysis. Examples include salts of thermally decomposable organic acids such as trichloroacetic acid, cyanoacetic acid, acetoacetic acid, and α-sulfonylacetic acid with the above-mentioned organic bases, and salts with 2-carboxycarboxamide described in U.S. Patent No. 4088.496. . Other base precursors described in British Patent No. 998,945, US Patent No. A22Q846, JP-A-50-22625, etc. can be used.

Further, the following compounds can be mentioned as compounds that generate a base by electrolysis. For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation. Through this reaction, carbonates of alkali metals and organic bases such as guanidines and amidines can be obtained extremely efficiently.

In addition, methods using electrolytic reduction include the production of amines by reduction of nitro and nitrone compounds, the production of amines by reduction of nitriles; the production of p-aminophenols and p-aminophenols by reduction of nitro compounds, azo compounds, azoxy compounds, etc. - Generation of phenylenediamines and hydrazines, etc. p-amine phenols, p-
7 Enylene diamines and hydrazines can be used not only as bases, but also directly as color image forming substances. Of course, it is also possible to generate a dialkali component by electrolysis of water in the coexistence of various inorganic salts.

Preferred specific examples are shown below, but the invention is not limited to these.

Lithium hydroxide, sodium hydroxide, barium hydroxide,
Sodium carbonate, cesium carbonate, sodium hydrogen carbonate,
Potassium carbonate, potassium hydrogen carbonate, sodium quinolate, dibasic sodium phosphate, dibasic potassium phosphate, tertiary
Sodium phosphate, tertiary potassium phosphate, potassium pyrophosphate, sodium metaborate, seaweed, aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, (OH3)2NH1(C2H5) 2
NH1C3H7NH2, HOC2H4111H2, (H
OC:2H4) 2Nl-1.

(HOC2H4)3N, H2NC2H4NH2, H
2N04) (8NH2, C) J3NHC2) (4NHC
H3, (CH3)214C3H6N(CH3)204-
f 3GH3 guanidine trichloroacetic acid, picoline trichloroacetic acid,
Morpoly/trichloroacetic acid, p-yluidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine carbonate, piperidine carbonate, morpholine carbonate, tetramethylammonium trichloroacetate, and the like.

Hydrochloric acid and/or base precursors can be used alone or in combination of two or more.

The amount of base and/or base precursor used in the present invention can be used within a wide range. When used in the photosensitive layer and/or the dye-fixing layer, it is appropriate to use them at a weight of 50 weight or less in terms of the total weight of the coating film, and more preferably from 0.01 weight to 40 weight. range is useful. Further, when used in the present invention after being dissolved in water, the concentration is preferably 0.005 mole// to 2 mole/1, particularly 0.05 mole//1.
A concentration of le/l to 1 mol θ/l is preferred. These added amounts have no direct relationship to pH. This is because if it is layered with a dye fixing material, etc., the base etc. will migrate to other layers.

In the present invention, water may be supplied by any method. For example, it may be ejected as a jet from pores, or it may be wetted with a web roller. It may also be used in the form of crushing water-filled pods, and is not limited to these and other methods. Further, a part of water may be incorporated into the material as crystal water or microcapsules.

The water used in the present invention is not limited to so-called 1-pure water, but also includes water in the widely customary sense. A mixed solvent may be used.Furthermore, a liquid containing an image formation accelerator, a hydrophilic heat solvent, etc., which will be described later, may be used.

When water is supplied externally, it is recommended to supply a constant amount of water to the photosensitive material and/or dye fixing material to ensure a uniform image)
However, as described later, when applying a small amount of water below the maximum swelling amount of the membrane, the image may be distorted due to uneven penetration of water into the membrane on the surface of the material. Unevenness tends to occur. Therefore, the water may be impregnated with a surfactant to completely improve the spread of water on the surface of the material.

The surfactant used in the present invention can be a surfactant known in the photographic industry and generally as a wetting agent. These surfactants are described in many well-known documents, such as Surfactant Handbook, Surfactant Science Series (
Edited by Martin GA Schick, Marcel Detzker Publishing, 1967) (5urfactant 5science)
5ene day (F, aited by Th, 4erti
n J, 5chick, Marcel Dakke
r Inc-1967)) etc. There are three types of surfactants: septionic, anionic, amphoteric, and nonionic, but any surfactant can be used as long as it satisfies the required YF described below. Two or more surfactants may be used in combination.

The amount of surfactant used in the present invention varies depending on the type of surfactant, but the surface tension of the aqueous solution is 4067ne/c.
It is desirable to add an amount that is below mv.

The amount of water in the present invention is at least 0.1 times the weight of the entire coating film of the light-sensitive material and dye fixing material, preferably 0.1 times the weight of the coating film to 1 times the swelling volume of the entire coating film. Within the range of the corresponding weight of water, more preferably from 01 times the weight of the total coating film to the weight of water corresponding to the maximum swelling volume of the total coating film to the amount of 'f3 of the total coating film. It is within the wholesale range after subtracting the amount.

The state of the film when it swells is unstable υ, and depending on the conditions, there is a risk that it may bleed locally and cause gold to form. A corresponding amount of water or less is preferred.

However, the effect of the present invention is the same as in the case where the amount of water is within the preferable range, in that the above-mentioned disadvantages only occur even when the amount of water is greater than the above amount, and the effect is exhibited.

The degree of swelling of the gelatin film varies markedly depending on the degree of dura, but the degree of dura is usually adjusted so that the film thickness at the most swollen state is 2 to 6 times the dry film thickness. be.

In the present invention, heating is performed, but since the present invention contains a relatively large amount of the solvent called water, the maximum temperature of the photosensitive material is 4A.
Aqueous solution in the food (various additives dissolved in the added water)
The boiling point C and C of the Minimum temperature H50℃
The above is preferable. The boiling point of water is 100°C under normal pressure, and heating above 100°C may cause water to evaporate and cause water to disappear. '1 It is preferable to supply high pressure steam.

In this case, since the boiling point of the aqueous solution also rises, the temperature of the photosensitive material also rises, which is advantageous.

The heating means may be a simple hot plate, an iron, a hot roller, a heat generating plate using carbon, titanium white, or the like. It is also possible to heat the photosensitive material and/or the dye-fixing material by providing an electrically conductive heating layer thereon and applying electricity to this layer.

In the present invention, after the step of heating the photosensitive material in the presence of water, a base and/or a base precursor, and an antifoggant to form an imagewise distribution of mobile dyes, the dye fixing layer is transferred from the photosensitive material to the dye fixing layer. Although it is possible to completely transfer the mobile dye, the effect of the present invention is particularly effective in a method in which the mobile dye is transferred to the dye fixing layer at the same time as the heating of the tank that forms the imagewise distribution of the mobile dye. It is played noticeably. For this purpose, the photosensitive material of the present invention has a photosensitive layer (I) containing at least silver halide, optionally an organic silver salt oxidizing agent, optionally a reducing agent, a dye-donating substance, and a binder on a support. and a dye fixing layer (n) which is formed of the layer (I) and is hydrophilic and diffusible and can hold the dye.

The above-mentioned photosensitive layer CI) and dye fixing layer (II) may be formed on the same support, or may be formed on at least one separate support. A dye fixing layer (n) and a photosensitive layer (1
) can also be torn off. For example, it is possible to uniformly heat the image after imagewise exposure and then peel off the dye fixing layer (n) or the photosensitive layer. Furthermore, when the photosensitive material coated with the photosensitive layer (I) on the support and the fixing material coated on the fixing layer (U>'r support) are formed separately, the photosensitive material is imagewise exposed. This is done by uniformly heating the fixing material (r) in the presence of water to transfer the more diffusible dye to the fixing layer Nu.

The dye fixing layer (II) can contain, for example, a dye mordant for dye fixation. A variety of mordants can be used as the mordant, with a particularly useful one being a polymer mordant. In addition to mordants, bases, base precursors, etc.
and a hot solvent. In particular, when the photosensitive layer CI) and the dye fixing layer (II) are formed on different supports, it is particularly useful to include a base or a base precursor in the fixing layer (II).

In the present invention, the light-sensitive material is used together with a dye-fixing element that fixes the dye, if necessary, and there are two types of forms in which the light-sensitive element and the dye-fixing element are formed on separate supports. One is a peel-off type, and the other is a type that does not require peeling. In the case of the former peeling type, picture 11! After exposure,
The coated surface of the photosensitive element and the coated surface of the dye-fixing element and 1! r: After overlapping and transfer image formation, the photosensitive element is immediately peeled off from the dye fixing element. Depending on whether the final image is of a reflection type or a transmission type, the support for the dye fixing element can be either an opaque support or a transparent support. Further, a white reflective layer may be coated if necessary. In the case of the latter type that does not require peeling, the photosensitive layer in the photosensitive element and the dye fixing J'VI in the dye fixing element are used.
It is necessary that a white reflective layer be interposed between the C and C, and the white reflective layer C may be coated on either the photosensitive element or the dye fixing element. The support for the dye-fixing element must be mounted on a transparent support.

Hereinafter, when the dye-fixing element is on a support separate from the photosensitive dye, it may be referred to as a dye-fixing material.

A typical configuration in which the photosensitive element and the dye-fixing element are coated on the same support is a configuration in which there is no need to peel off the photosensitive element from the image-receiving element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include 1, for example, transparent or opaque support/photosensitive layer/white reflective layer/dye fixing layer/transparent support/dye fixing layer/white reflective layer/photosensitive layer, etc. can be mentioned.

Another typical form in which a photosensitive element and a dye fixing element are coated on the same support includes, for example, Japanese Patent Application Laid-Open No. 56-67840.
, Canadian Permit No. 674082, United States Permit No. 674082, United States Permit No. A73
As described in No. Q718, there is a form in which part or all of the photosensitive element is peeled off from the dye-fixing element, and a peeling layer is coated at an appropriate position. .

When the light-sensitive element and the dye-fixing element are on the same support, they will simply be referred to as light-sensitive materials in the following.

The photosensitive element or the dye fixing element may have a conductive heating layer as a heating means for thermal development or wide range transfer of the dye.

The silver halides used in the photosensitive material of the present invention include silver chloride, silver chloride, silver iodine, silver chlorobromide, silver chloroiodide, silver iodine, and silver chloride iodobromide. Either is fine.

The halogen composition of the particle circle may be uniform, or it may have a multiple structure with different groups 5 on the surface and inside (Japanese Patent Application Laid-open Nos. 57-154232, 58-108533, 5
No. 9-48755, No. 59-52237, US Patent No. 4.43a 048 and European Patent No. 10Q984
issue). (2) Tabular grains with a grain thickness of 0.5 μIn or less, a thickness of at least 0.06 μm, and an average aspect ratio of 5 or more (US Patent No. 4414.310, No. 4.43 &
No. 499 and OLS No. a241,6
46A1, etc.), or monodispersed emulsions with a nearly uniform particle size distribution (JP-A-57-178235, JP-A No. 58-10)
No. 0846, No. 58-14829, International Publication No. 8310
2338A1, European ζ 64412A3 and 83377A1, etc.) may also be used in the present invention. Two or more types of halides having different crystal habit, halogen composition, particle size, particle size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing monodisperse emulsions of 2ff1 or more having different grain sizes.

The grain size of the silver halide used in the present invention preferably has an average grain size of 0.001 μm to 10 μm.
More preferably, the thickness is from 0.001 μm to 5 μm. These silver halide emulsions may be prepared by any of the acidic method, neutral method, or ammonia method, and the reaction method of soluble silver salt and soluble halide salt may be one-sided mixing method or simultaneous mixing method. Or any combination of these may be used. Back-mixing method where particles are formed under silver ion excess, or pAg
The Chondral double-jet method, which maintains a constant value, can also be used. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (% 1985-142329, 55
-158124, U.S. Patent No. 365 Q757, etc.)
.

Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, U.S. Patent No.
No. 1.094684).

In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, and Japanese Patent Publication No. 47-1
Organic thioether derivatives described in No. 1386 or sulfur-containing compounds described in JP-A-53-144319 can be used.

In the process of particle formation or physical ripening, moldium salts, zinc salts, lead salts, thallium salts, etc. may be co-present.

Further, for the purpose of improving high-light failure and low-light failure, water-soluble iridium salts such as iridium chloride (LIT, IV) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

The silver halide emulsion may be subjected to soluble salt gold removal after precipitation or physical ripening, and thus can be subjected to the Tardel water washing method or the precipitation method.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known sulfur sensitization methods, reduction sensitization methods, U metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be improved by performing the chemical sensitization in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526, JP-A-58-215644).
.

The silver halide emulsion used in the present invention may be of the surface latent image type in which a latent image is mainly formed on the surface of the grains, or may be of the internal latent image type in which the latent image is formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat. No. 2,592,250, U.S. Pat. Preferred nucleating agents for combination in the present invention are U.S. Pat.
．． 24 to No. 037, No. 4255511, No. 426
a031, 4276.364 and OLS No. 2
It is described in No. 635316, etc.

The coating amount of the photosensitive silver halide used in the present invention ranges from ITny to 10.97 m' in terms of silver.

In the present invention, an organic metal salt relatively stable to light can be used in combination with the photosensitive silver halide as an oxidizing agent. In this case, photosensitive silver halide and organic gold [
4 requires a state of contact or a close distance of +111/. Among such organic metal salts, organic silver salts are particularly preferably used. Such organic metal properties are effective when developing a photothermographic material by heating it to a temperature of 50° C. or higher, preferably 60° C. or higher.

Organic compounds that can be used to form the above organic silver salt coordinating agent include aliphatic or aromatic carbon nt,
Examples include thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds.

Silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, cabric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, lylunic acid, and oleic acid. Typical examples include silver salts derived from adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid, propiolic acid or camphoric acid. Silver salts derived from these fatty acids substituted with a norogen atom or a hydroxyl group, or aliphatic carboxylic acids having a thioether group can also be used.

Aromatic carboxylic acid and other carboxyl group-containing 1
Examples of the steel core of arsenic compounds include benzoic acid, 35-dihydroxybenzoic acid, o-, to- or p-methylbenzoic acid,
24-dichlorobenzoic acid, acetamidobenzoic acid, p-
Phenylbenzoic acid, gallic acid, tannic acid, phthalic acid,
Representative examples include silver salts derived from terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid, or 3-carboxymethyl-4-methyl-4-thiazoline-2-thione. As a silver salt of a compound having mercapto or thiocarbonyl at, 3-mercapto-4
-Phenyl-LZ 4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercapto(nzothiazole), S-alkylthioglycolic acid (alkyl group has 12 to 22 carbon atoms), dithiocarboxylic acid such as dithioacetic acid Acids, thioamides 1 such as thiostearamide P, 5-carboxy-1
-Methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptoindioxazole, mercaptooxadiazole or 3-amino-5-benzylthio-L2.4-triazole, etc. U.S. Patent No. 41
Examples include silver salts derived from mercapto compounds described in No. 21274.

As a silver salt of a compound having an imino group,
30270 or 45-18416, or derivatives thereof, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, butylcarboimidobenzotriazole Carboimidobenzotriazoles, such as nitrobenzotriazoles described in JP-A-58-118639, sulfoin-citriazole, carboxybenzotriazole or its salt, or hydroxy-in-citriazole, etc., described in JP-A-58-118,638, U.S. Pat. 1 described in No. 422Q709.
Representative examples include silver salts derived from 24-triazole, IH-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof.

Furthermore, F Silver salts of carboxylic acids having the formula can also be used in the present invention.

The above-mentioned organic silver salts can be used in combination in amounts of 0.01 to 10 mol, preferably 0.01 to 1 mol, of silver halide (photosensitive). The total coating amount of photosensitive silver genide and organic silver salt is 5011 Ig to 1011
/l? ? is appropriate.

The silver halogenide used in 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. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Sol nuclei, penzimida pool nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a nucleus containing a ketomethylene structure, such as a girabulin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus.
5-6H heterocyclic nuclei such as 4->one nucleus, thiazolidine-24-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus can be applied.

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, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 363-72)
1, etc.), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 74a510, etc.), cadmium salts, azaindene compounds, etc. may also contain gold. U.S. Patent No. 3,615,613, U.S. Patent No. 3
．． No. 615.641, No. a617.295, No. 3
The combinations described in No. 635.721 are particularly useful.

In order to incorporate these sensitizing dyes into a silver halide photographic emulsion, they may be directly dispersed in the emulsion, or they may be dispersed in a solvent such as water, methanol, ethanol, acetone, methyl cellosolve, etc. alone or in a mixture. It may be dissolved in a solvent and added to the emulsion. Alternatively, after dissolving them in a substantially water-immiscible solvent such as gold phenoxyethanol, they may be dispersed in water or a hydrophilic colloid, and this dispersion may be added to the entire emulsion. Unfortunately those sensitizing dyes? It is also possible to mix it with a lipophilic compound such as a dye-donating compound and add it at the same time. 1. When dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately, or a mixture may be dissolved. When added to an emulsion, they may be added simultaneously as a mixture, separately, or simultaneously with other additives.

The timing of addition to the emulsion may be during or before chemical ripening, and US Pat.
It can also be used before and after nucleation of silver halide grains according to No.

The amount added is generally about 910-8 to 10 moles per mole of silver halide.

In the present invention, when photosensitive silver halide is reduced to silver under high temperature conditions, a compound that generates or releases a mobile dye in response to or inversely to this reaction, i.e., a dye-donating compound, is used. Contains sexual substances.

Next, the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. A method using this coupler, in which an oxidized product of the developer produced by the redox reaction between the silver salt and the developer reacts with the coupler to form a dye, is described in numerous documents. Specific examples of developers and couplers include:
For example, T.H.James
The Theory of the Photographic Process (Th8 thaorv of the ph)
otographicprOcess) 4th edition
(4th, Ea,), 291-334-<-
It is described in detail in J., 2 and 354-361 BA-J, Makoto Kikuchi, 1 Photo Chemistry, 4th edition (Kyoritsu Shuppan), 284-295 R-J.

A dye silver compound in which a dye is combined with an organic silver salt and a dye can also be cited as an example of the dye-donating substance. Specifics of dye silver compounds 11 are published in Research Disclosure magazine, May 1978 issue, pages 54-58, (HD-1, 6966)
Etc. VC is listed.

Further, an example of the dye-donating substance is an azo dye used in a heat-developable silver dye bleaching method.

An example of an azo dye and a bleaching method are disclosed in U.S. Patent No. 42.
No. 34x957, Research Disclosure Magazine, 19
April 1976 issue, pages 30-32 (RD-14433)
etc. are written & described.

Also, US Patent No.: 1985565, 4 (122,
This can be said to be an example of the leuco dye-donating substance described in No. 617, etc.

Another example of a dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner.

This type of compound can be represented by the following general formula (Ll).

(Dye - to cause a difference in the diffusivity of the compound represented by (Dye-X)-Y, or Itj
, Dyef is released, and the released Llye and (Dye-X
). -Represents a group having properties that cause a difference in diffusivity compared to Y, 0 represents 1 or 2,
When O is 2, the two Dye-Xfis may be the same or different.

Specifics (?) of the dye-donating substance represented by general formula (Ll)
As lJ, for example, a dye layer developing agent containing a hydroquinone developer and a dye component is disclosed in US Pat. No. 313,
! , No. 764, No. 3362.819, No. i:
No. 597.200, No. 3544.545, No. 34
It is described in No. 82972, etc. Furthermore, a substance that releases all of the diffusible dye through an intramolecular nucleophilic substitution reaction l/C is disclosed in JP-A-51-61618, etc., which releases all of the diffusible dye through the intramolecular winding +'9 reaction of the isoogisazolone ring. The substance is described in Japanese Patent Application Laid-Open No. 49111.628.

In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is neither released nor diffused in areas where development has occurred. A color-emitting compound? The rlW form Vζ, which does not have the ability to release a dye, is made to coexist with a reducing agent or its precursor, and after development, it is reduced by the reducing agent that remains without being oxidized to produce a diffusible dye? He also devised a method for producing hot water, and details of the dye-donating substance used therein were published in JP-A No. 53-11Q827.
It is described in No. 54-13Q927, No. 5G-16, No. 342, and No. 53-35,533.

On the other hand, is there a diffusible dye in the area where development has occurred? A substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized developer is disclosed in British Patent No. 133Q524 and Japanese Patent Publication No. 48-3916.
No. 5, U.S. Patent No. 344: L940, etc., a substance that generates a diffusible dye through the reaction of a coupler having a diffusion-resistant group and a total leaving group with an oxidized developer is disclosed in the U.S. Patent No. permission number a
227.550 etc.

° Also, in the method of using these colored soul statues, the present (:
J! Since contamination of images caused by 1ψ decomposition products of drugs becomes a serious problem, the developing agent is not required at all during this period in order to completely improve the image quality. Dye-releasing ornaments whose materials themselves have reducing properties have also been devised. Representative examples are shown below along with literature. The definition of h in the general formula is described in each literature.

U.S. Patent No. 192a312 etc. U.S. Patent No. t053312 etc. Ballast U.S. Patent No. 405 to 428 etc. JP 51-104343 JP 51-104343 ○H Ba] 1st JP 51-104,343 Research Disclosure, t 17465 U.S. Patent No. 1725,062 H U.S. Patent No. A72 & 113 U.S. Patent No. 3.441939 JP 58-116537 The dye moiety represented by Dyθ is derived from azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, etc. The dye portion may be one whose wavelength has been temporarily shortened or a precursor. Specific examples of dye moieties released from dye-donating compounds are described in the aforementioned Japanese Patent Application No. 57-1942.
Examples include those described on pages 37 to 59N of Publication No. 02, and the chelate color; t described in JP-A-53-35533.

Any of the various dye-providing substances described above can be used in the present invention.

Specific examples of imaging materials for use in the present invention are described in the patent documents cited above. Since it is not possible to list all the preferred compounds here, some of them will be shown as examples.

The compounds described above are just examples, and the invention is not limited thereto.

In the present invention, oil-soluble yarn 7JO agents such as dye-donating substances and image-forming accelerators described below are described in US Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 322.027. In that case, all of the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl esters (e.g., butyl 7-thalerate, dioctyl phthalate), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), esters of citrate (e.g., acetyl tributyl citrate) , benzoic acid ester (octyl benzoate)
, alkylamibis (e.g. diethyl laurylamide),
High boiling point organic solvents such as fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesate esters (e.g. tributyl trimesate), or organic solvents with a boiling point of 30°C to 160°C, such as ethyl acetate, acetic acid Lower alkyl acetates such as methyl, ethyl propionate, secondary butyl alcohol,
After being dissolved in methyl isobutyl ketone, β-ethoxyethyl acetate, methylseron rubacetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using polymers described in No. 3 can also be used. Various surfactants can also be used to disperse the dye-providing substance in the hydrophilic colloid, and these surfactants include Those listed as surfactants elsewhere in the specification may be mentioned.

The content of the high boiling point organic solvent used in the present invention is 10.9 or less per 1 g of the dye-donating substance used.

Preferably it is 5g or less.

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

In the present invention, it is preferable to include a reducing substance in the light-sensitive material. As the reducing substance, in addition to those generally known as reduction methods, the above-mentioned dye-donating substance having an itosome property can be used.
t■ is also included. Also included are rust source precursors that do not themselves have reducibility but develop reductive properties due to the action of nucleophiles and heat during the dust image process.

Examples of reducing agents used in the present invention include inorganic N groups such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane-amine complexes, hydroquinones, and aminophenols. songs, including catechols, p-phenylenediamines, 3-pyrazolidinones, hydroquintetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., by T.H.
The Theory of the Photographic Process, by T-H-James
of the photographic processes
s'') 4th edition, pp. 291-334 can also be used. Also, the reducing agent described in JP-A-56-138,736, JP-A-56-138,736;
No. 7-40,245, U.S. Pat. No. 4.33 Q 617
Is it listed in the issue? ψThe original side recursor can also be used.

Combinations of various developers can also be used, such as those disclosed in US Patent No. 303a869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01-20 mol, t! +V is preferably 0.1 to 10
It is a mole.

The present invention includes 1. IIJJ imaging promoters can be used. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive material layers. It has the function of promoting the movement of the dye from the dye fixing layer to the dye fixing layer, and from a physicochemical function, it has the function of promoting the movement of the dye from the above-mentioned base or base precursor, nucleophilic compound, oil, hot solvent, surfactant, silver or silver ion. It is classified as a compound that has interactions. However, these groups of substances generally have multiple functions and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators other than bases or base precursors are classified by function and 11 specific examples are shown for each. However, this classification is for convenience, and in reality they are often have multiple functions.

(a) Nucleophilic compounds water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, human-1 radines, hydrazides, oximes, human-10 xamic acids, sulfonamides, activated methylene compounds, Examples include alcohols and thiols, and salts or precursors of the above compounds can also be used.

(lI) Oil A high boiling point organic solvent (so-called plasticizer) used as a solvent during emulsification and dispersion of a hydrophobic compound can be used.

(C) Thermal Solvents These are isomers at ambient temperature, and they melt near the development temperature and act as a solvent; urea and urethane, respectively.

Amide neck, pildins, sulfonamides, sulfones,
Compounds such as sulfoquinone, esters, ketones, and ethers that are solid at 40°C or lower can of course be used.

(d) Surfactant r+8 Pyridinium [a
, 77monium salts, phosphonium salts, JP-A-59-
Examples include polyalkylene oxy/do metals described in No. 57231@F.

Examples include imides, nitrogen-containing heterocycles described in Japanese Patent Application No. 58-51657, thiols, thioureas, and thioether compounds described in Japanese Patent Application No. 57-222247.

The image formation accelerator may be incorporated into either the light-sensitive material or the dye-fixing material, or may be incorporated into both. The embedding layer may also be incorporated into the emulsion layer, intermediate layer, protective layer, dye fixing layer, and any layer adjacent thereto. The same applies to the case where the photosensitive layer and the dye fixing layer are all on the same support.

The image formation accelerator can be used alone or in combination of more than one type, but generally a greater accelerating effect can be obtained when several types are used in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in order to always obtain a constant image quality despite fluctuations in processing temperature and processing time during development.

The development stopper mentioned here is a compound that completely neutralizes the base or reacts with the base to stop the development due to the base concentration in the film after proper development, or a compound that interacts with silver 2 and silver salt to stop the development. It is an inhibitory compound.

Specific examples thereof include acid precursors that release prg/ when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors.

Examples of acid precursors include oxime esters described in Japanese Patent Application No. 58-216928 and Japanese Patent Application No. 59-48305, compounds that release all of the acid by Rossen rearrangement described in Japanese Patent Application No. 59-85834, and the like. Examples of electrophilic compounds that undergo a substitution reaction with a base when heated include the compound Nade described in Japanese Patent Application No. 59-85836.

Compounds that release mercapto compounds upon heating are also useful;
No. 9-268926, No. 59-246468, No. 60
-26038, 60-22602, 60-26
No. 039, No. 60-24665, No. 60-29892
There is a compound described in No. 59-176350.

The above-mentioned development stoppers are particularly effective when all base precursors are used, which is preferable.

In that case, the ratio of base precursor/IIW precursor (
The value of molar ratio) is preferably 1/20 to 20/1, and 11
More preferably 5 to 5/1.

Further, in the present invention, it is possible to use a compound that activates development and simultaneously stabilizes the image.

Among them, isothiuroniums typified by 2-hybyloxyethylinthiuronium trichloroacetate described in U.S. Patent No. A30L678, U.S. Pat.
1,8-16-thioxaoctane)bis(isothiuronium trichloroacetate) described in No. 66Q1i70
Bis(inchuronium) such as, West German Patent Publication No. 21
Thiol compounds described in 62.714, U.S. Pat.
．． Thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in No. 012260, bis(2-amino- Compounds having α-sulfonylacetate as the acidic moiety, such as 2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazoliumphenylsulfonylacetate, are preferably used.

Furthermore, the azurthioether and blocked biazolinthione compounds described in Belgian Patent No. 76&071 and the 1-aryl-1
-Carbamyl-2-tetrazoline-5-thione compound, and other US Patent No. λ839. Compounds described in CI No. 41, CI No. 884 Tun No. 788, and CI No. 3877.940M are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are L24-triazole,
IH-tetrazole, thiourashi 1, shallow 4-thiadiazole-2-thiol, 3-mercapto-1,24-triazole, bis(dimethylcarbamyl) disulfide 1
．． Examples include 6-methylthiouracil and 1-phenyl-2-tetraazoline-5-thione. Is the toning agent effective for cargo shown in black? It is a compound with 1 that forms a vine.

Yoshiari's color toning agent varies depending on the type of heat-developable photosensitive material, processing conditions, the desired image, and the number of steps in the song, but in general .'C = 0.001 to 0.1 mole fp) to 1 mole of silver of the original material A.

The binders used in the present invention may be contained alone or in combination. It is best to use a hydrophilic binder for this binder.

As a hydrophilic binder・7. f. Transparent or translucent water-based binders are typical, and 5.
Synthetic polymeric materials such as water-soluble rtZ') vinylated compounds such as ribinylbilolibin and acrylamide polymers. Other synthetic polymeric substances +='c in the form of latex,
Especially the size of photographic materials? There are dispersed vinyl compounds that increase. In addition, Research Disclosure (R
esearch Disclosure) 1978 1
The compounds described in Section ① A of February issue, page 26 can be used.

The binder of the photosensitive material is applied in an amount of 20 g or less per 1 m', preferably 10 g or less, and more preferably 7 g.
The following are appropriate.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 cc or less of solvent to binder III, preferably 0.5 cc or less, more preferably 0.30C. The following are appropriate.

The photographic light-sensitive material and dye fixing material used in the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde 1, cryoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2
, 3-dihydroxydioxane, etc.), active vinyl compounds (1,a5-1reacryloyl-hexahibirow〇-triacin% L3-vinylsulfonyl-2-fbanol, L2-bis(vinylsulfonylacetamide)-4)
ethane, etc.), active halogen compounds (2,4-dichloro6-:bioxychloride/-1a5- 7)y, etc.), mucohalogen acids, (mucochloric acid, mucophenoxychloroic acid, etc.) , etc. can be used alone or in combination.

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related Contains film or resin materials. A paper support laminated with a polymer such as +19 polyethylene can also be used. Jellyester 1 described in US Pat. Nos. 3,634,089 and 3,725,070 is preferably used.

Among the photosensitive materials used in the present invention, in particular, the general formula (L
When containing a dye-providing substance represented by l), if the dye-providing substance is colored, an anti-irradiation or anti-nolation substance or various dyes may be further contained in the light-sensitive material. Although it is not so necessary to increase the sharpness of the image, in order to improve the sharpness of the image,
Contains filter dyes, absorbent substances, etc., as described in the specifications of -3f'i92, U.S. Patent Nos. 3.253921, 2527, 583, and 29-56879. be able to. In addition, these dyes are preferably thermally decolorizable; for example, as disclosed in U.S. Pat.
．． No. 769019, No. a745,009, No. 3
Dyes such as those described in No. 615,432 are preferred.

The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials, layers below the Δg optical layer, such as D antistatic layer, conductive layer, protective M, intermediate layer,
It can contain all of the AH layer, release layer, etc. For various additives, see Research Disclosure Magazine Vol. 17.
0, additives described in Haruka No. 77029, June 1978, such as plasticizers, sharpness improving dyes, AH dyes,
Additives include sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, and anti-fading agents.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, the photosensitive element used in the present invention has at least three layers, each sensitive to a different chromaticity region. It is necessary to have a silver halide emulsion layer with a

Pf? , /l, a combination of at least three light-sensitive silver halide emulsion layers, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion. Combination of layer 3 and infrared light sensitive emulsion layer.

Examples include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer. Incidentally, the infrared light-sensitive emulsion layer refers to an emulsion layer containing gold that is sensitive to light of 700 nm or more, particularly 740 nm or more.

The light-sensitive material used in the present invention may have two or more layers, depending on the sensitivity of the entire emulsion, if necessary.

The above valley emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer has a dye donating substance that totally releases or forms a hydrophilic dye for yellow, and a dye donating substance that totally releases or forms a hydrophilic dye for magenta. It is necessary to contain at least one of a dye-donating substance and a dye-donating substance that releases or forms a cyan hydrophilic dye. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain all dye-donating substances that release or form hydrophilic dyes of different hues.

A mixture of two or more dye-providing substances having the same hue may be used depending on the user's wishes. Particularly when the dye-providing substance is colored from the beginning, it is advantageous for the VC to contain one dye-providing substance in a layer separate from this emulsion layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention may contain gold films as auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matting agent layer, if necessary.

In particular, the protective layer (PC) usually contains an organic or inorganic matting agent to prevent adhesion.

Also, is there a mordant, UV absorber, etc. in this protective layer? May be included. Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent, a UV absorber, and a white pigment such as T10□ to prevent color mixing. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.

In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using any known sensitizing dye to obtain the desired spectral sensitivity.

The dye fixing element used in the present invention has at least one layer containing a mordant. When the dye fixing layer is located on the surface, a protective layer can be further provided if necessary.

Furthermore, a water-absorbing layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain the dye transfer aid as required, or to completely control the dye transfer aid. These layers may be in contact with the dye fixing layer, or may be an intermediate layer? It may also be coated through.

The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary.

In addition to the above-mentioned layers, the dye fixing element used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.

One or more of the above layers may include base additives and/or base precursors to promote dye transfer, parentheses, aqueous heat solvents, antifade agents to prevent dye mixing, UV absorbers, In order to completely increase the degree of stability, a fused vinyl compound, a fluorescent whitening agent, etc. may be used.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, cellulose derivatives, starch, natural substances such as polysaccharides such as acacia, dextrin, pullulan, polyvinylpyrrolidone,
Synthetic polymeric materials such as water-soluble JIJ vinyl compounds of acrylamide polymers, etc. are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

In addition to the above, the dye fixing element may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc. depending on the purpose. These layers may be coated not only in the dye-fixing element but also in the photosensitive element. The structures of the above-mentioned reflective layer, neutralization layer, and neutralization timing layer are described in, for example, U.S. Pat.
It is described in Canadian Patent No. 3362821, Canadian Patent No. 341 & 644, Canadian Patent No. 92 & 559, etc.

In general, the dye-fixing element may contain the above-described water or the like used in the present invention in the dye-fixing layer, or may be contained in a separate layer as a whole.

The dye fixing layer in the present invention includes a dye fixing layer used in heat-developable color light-sensitive materials, and can be arbitrarily selected from commonly used mordants, but among them, polymer mordants are preferred. Here, the 4-limer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation group thereof, and the like.

Regarding the vinyl monomer one unit Kanakura polymer having a tertiary amine group, Japanese Patent Application No. 169012/1982, %Gan Sho 5
8-166135, etc., and specific examples of polymers containing one unit of vinyl monomer having a tertiary imidazole base include Japanese Patent Application Nos. 58-226497 and 58-2.
No. 32071, US Pat. No. 4,282.305, US Pat. No. 411-124, US Pat. No. 314a061, and the like.

Preferred examples of polymers containing one vinyl nitrate unit having a quaternary imidazolium salt include British Patent No. 205.
alO1, 2093041, 1594.9
No. 61, U.S. Patent No. 4,124,386, and U.S. Patent No. 4. ],
No. 15.124, No. 4.273,853-i to No. 1.45 (No. 1224, JP-A-48-28-225)
It is stated in the number etc.

Other preferred specific examples of vinyl monomer monounit polymer polymers containing quaternary ammonium salts include the United States! Patent No. &70α690, Patent No. 3.89&088, Patent No.:
No. 1953995, Japanese Patent Application No. 58-166135, No. 5
No. 8-169012, No. 58-232070, No. 58
-232072 and 59-91620.

In the present invention (V), the transparent or opaque heat-generating element in the case where electrical heating is employed as the developing means can be made by utilizing all conventionally known techniques for producing resistive heat-generating elements.

As a resistance heating element, two methods are considered: one is to fully utilize a thin film of an inorganic material exhibiting semiconductivity, and the other is to fully utilize a thin film of an organic material in which conductive fine particles are dissolved in a binder.

The monthly fee that can be used in the method mentioned above is silicon carbide,
Examples include molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTG thermistors, tin faecium, and zinc oxide, and transparent or opaque thin films can be made by known methods. In the latter method, conductive fine particles such as carbon black, graphite, etc. are whole rubber.

By dispersing synthetic polymers in gelatin, it is possible to create an entire resistor with the temperature characteristics of Shintaku. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, or the like.

An example of the positional relationship between the heating element, the sensor f, and the element is shown below.

Heat-generating element/support/photosensitive element support 7 Heat-generating element/photosensitive element support/heat-generating element/intermediate layer/photosensitive element support/photosensitive element/heat-generating element support/photosensitive element/intermediate noodle 7 Heat-generating element, ■In the invention For the I+ & light layer, dye fixing layer, protective layer, intermediate layer, undercoat layer, back layer, and other layers, 3. Complete preparation of each coating solution (-1 immersion method, air knife method, curtain coating method. A light-sensitive material can be prepared by sequentially coating a support on a support using a special coating method such as the hopper coating method described in U.S. Pat. No. 3,681,294 and drying.

Additionally, if necessary, see US Pat. No. 276L791 and British Patent No. 837. (Two or more layers can also be applied all at the same time by the method described in the '195 specification.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light and sound can be used. In general, light sources used for normal color printing include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, and light-emitting diodes (LEDs).
Various light sources such as can be used.

In accordance with the present invention, when a transfer step is included, a dye transfer aid may be used to fully facilitate the transfer of the imagewise distributed mobile dye from the photosensitive layer to the dye fixing layer.

In a system in which all the transfer aids are externally supplied, the dye transfer aid may be water used in the present invention as defined above, preferably an aqueous solution of an antifoggant or a surfactant, or a caustic solution, caustic potash, or an inorganic alkali. A basic aqueous solution containing a metal salt and/or an organic base is used. As these bases, those described in the section of the image formation accelerator are preferably used.

In addition, organic solvents such as methanol, N,N-dimethylformamide, acetone, and diisobutyl ketone, antifoggants for these organic solvents, or the base and/or
Alternatively, a mixed solution of base precursors and the like can be used. The dye transfer aid may be used in a method in which the dye fixing material or the photosensitive material or both are wetted with the transfer aid.

If the transfer aid is incorporated into the light-sensitive material or dye fixing material, it is not necessary to supply the transfer aid from the outside, but both may be used in combination. The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or
Inner M-g may be used as a precursor that releases all of the solvent at high temperatures. More preferably, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature is incorporated into the light-sensitive material or dye-fixing material. Parent, water-based thermal solvent is photosensitive material,
It may be incorporated into either of the dye fixing materials, and both may contain internal M.
You may let them. The layer containing the dye may be an emulsion layer, an intermediate layer, a film-holding layer, or a dye (6) fixed layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyridines, amides 1, sulfonamides, imi) 1, alnyls, oximes, and other heterocycles.

When the development process and the transfer process are carried out separately, the heating temperature is approximately 0°C to approximately 250°C, and the heating temperature is approximately 0°C.
to about 180°C are useful. The heating temperature in the transfer process is
Temperature to room temperature during heat development process 50
Although transfer is possible at a temperature of about 10° C., it is particularly preferable to transfer the film at a temperature about 10° C. lower than the temperature of the thermal development step Vc.

Examples of methods for completely applying the dye transfer aid to the photosensitive layer or the dye fixing layer include a roller coating method or a wire bar coating method as described in JP-A No. 58-55907, and a wire bar coating method as described in JP-A No. 58-55908. A method of coating a dye-fixing material with water using a water-absorbing member as described in 2003, and a method of coating a dye-fixing material with water using a water-absorbing member as described in Japanese Patent Application No. 58-55906. Method for completely applying dye transfer aid by forming, Japanese Patent Application No. 58-5591
Is there a bead between the water repellent roller and the dye fixing layer as described in issue 0? Various methods can be used, including a method in which the dye transfer aid is completely applied by forming the pigment, a dipping method, an extrusion method, a method in which it is applied by ejecting it as a jet from pores, and a method in which it is applied by crushing the pores.

The amount of dye transfer aid is within the range as described in Japanese Patent Application No. 58-37902. You can measure and apply it in advance, or give it enough and then apply pressure with a roller etc.
Squeeze it out or heat it? In addition, it can be dried and used in its entirety.

For example, in the dye fixing material may dye transfer aids be added in the above method, such as water used in the present invention? There is a method in which the dye transfer aid is applied, passed through a pressurized roller to squeeze out excess dye transfer aid, and then superimposed on a photosensitive material.

The pressure when overlapping the heat-developable photosensitive material and the dye-fixing material and bringing them into close contact depends on the embodiment and the materials used. - is appropriate (for example, Japanese Patent Application No. 58-5
5691).

Various methods can be used to apply full pressure to the heat fn, +'M photosensitive material and the dye-fixing material, such as passing a pair of rollers (t)11 through, and pressing using a plate with good smoothness. Can be used. The advantage is that when applying pressure, the rollers and plates can be heated from room temperature to the temperature range of the heat development process. In this case, transfer can be performed at a temperature ranging from humidity to room temperature in the heat development process, but it is particularly preferable to use a temperature 1 that is about 10° C. lower than the temperature used in the heat development process.

Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in more detail.

Example 1゜ This article describes how to make benzotriazole silver emulsion.

Seratin 28.9 and Incitriazole 13.2 II
It was dissolved in 300% of total water. This solution was kept at 40°C and stirred. A solution of 17 g'z of silver nitrate dissolved in 100 ytl of water was added to this solution over 2 minutes.

This benzo) I) pHyk adjustment of the azole silver emulsion,
Sedimentation was performed to remove excess salt. Then pHk6.3
0, a benzotriazole silver emulsion gold with a yield of 400.9 was obtained.

How to make silver halide emulsion for the 5th layer and 1st layer? Spread.

A well-stirred aqueous gelatin solution (containing 2 liters of gelatin and 39 liters of sodium chloride in 1,000 ml of water, kept at 75°C), 600 ml of an aqueous solution containing sodium chloride and potassium bromide, and an aqueous solution of silver nitrate ( 80.59 moles of nitric acid dissolved in 600 d of water) were added at the same time over a period of 40 minutes at an equal flow rate.In this way, a monodisperse cubic salt-embodied silver emulsion with an average grain size of 0.40 μm (
(50 moles of bromine) All preparations were made.

After washing with water and desalting, sodium thiosulfate 5■ and 4-human 10
xy-6-methyl-La3a, 7-chitrazaisodene 2
All chemical sensitization was carried out at 60'C with the addition of 0.1 (I-R4).The yield of the emulsion was 600!J.

Next, we will explain how to make silver halide emulsions for 3j~.

A well-stirred gelatin aqueous solution (20 g of gelatin and chloride in 1000 m of water) 3. Q-contains, 7
An aqueous solution containing all of sulfur chloride and potassium bromide (kept at 5°C) and a silver nitrate aqueous solution (620.5 g mole of 6A completely dissolved in 600 d of water) were simultaneously mixed at VC40. Added at equal flow rates over min iK. In this way, a monodisperse cubic salt-based button emulsion (80 mol % of bromine) with an average particle size of 0.35 μm was prepared.

Washing with water, desaturation, sodium thiosulfate 5■, 4-hydroxy-6-methyl-La3a, 7-tetrazaindene 20
■? All chemical sensitization was carried out at 60°C. The yield of emulsion was 600 g.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

Yellow dye-donating substance (A) k5%, 0.5y of sodium succinate 2-ethyl-hexyl ester sulfonate as surfactant, triisononyl phosphate 10
gtl", add 30ml of ethyl acetate, and add about 60ml of ethyl acetate.
The mixture was heated to 44° C. in a heating bath to form a homogeneous solution. After stirring and mixing this solution with lime-treated gelatin 10 soluble 7i100F, use a homogenizer for 10 minutes at 110,000 rpm.
It was dispersed. This fractional liquid is called a dispersion of an all-yellow dye-providing substance.

Magenta dye-donor substance (8) A dispersion of magenta dye-donor substance was prepared in the same manner as above, except that tricresyl phosphate was used as a high-boiling solvent. Had made.

A cyan dye-providing substance (C)' was prepared in the same manner as the yellow dye dispersion.

Using these materials, a color photosensitive material with a multilayer structure as shown in the following table was prepared.

Dye-donating substance (B) for (C) OC16H33(n) (D-1) (D-2) (D-3) 2H5 Next, we will discuss how to make the dye fixing material.

Gelatin 6319 was dissolved in 130 g of a mordant having the following structure and 2.5.9' of L2-bis(vinylsul7onyl acetamido)ethane in 1300 m of water to give a wet film thickness of 42 μm on a paper support laminated with polyethylene. was applied and then dried.

Furthermore, on top of this, 35g of gelatin, 4g of sodium metaborate
1 liter of aqueous salt 31-8 (liquid t-17 dissolved in 10% water)
A dye fixing material was prepared by coating and drying to a wet film thickness of μm.

G and R, which use a tungsten light bulb as the color photosensitive material with a multilayer structure, and whose density changes continuously.

IFI three-color separation filter (G is 5QO to 600nm.

B is a 600-700 nm hand nomos filter, I
R was constructed using a filter that transmits at least 700 nm)
The entire image was exposed to light at 500 lux for 1 second.

20w1/rr on the emulsion side of this exposed photosensitive material? Water (Table 1αA) was supplied with a wire bar, and then the dye-fixed wood (material) was shielded so that the 121 side was in contact with the wire bar.

When the dye fixing material is peeled off from the light-sensitive material after heating for 25 seconds using a heat roller whose temperature is adjusted so that the temperature of the water-absorbed film is 90 to 95°C, G% appears on the fixing material.
Yellow, corresponding to the R, IFt color separation filter.
Magenta and cyan images were obtained. Maximum density CD of each color
) and 7# low density (Dm) ax total Maquis reflection density L (meter (hD-st9) k).

Next, all operations and treatments were carried out in exactly the same manner as above, except that 2 aqueous solutions containing the antifogging agent of the present invention (B-G of Cloth-1) were used instead of water, and the results shown in Table 1 were obtained.

Note that the composition of the aqueous solution AB-G of the present invention is 20 g of the exemplary compound of the present invention, succinic acid-2-ditylhexisester sulfonic acid -l'1! ? The mixture was dispersed for 24 hours in a Gecolloid Mill of 100 parts of water, and then diluted to obtain a solution having the concentration shown in Table 1. The composition of the comparative sample aqueous solution mA is the same as B-G except that it does not contain any antifoggant.

From the above results, it was found that when the compound of the present invention is used, turnip IJ' (Il-) can be effectively suppressed and clear images can be obtained.

Example 2゜Photosensitive material, dye fixing material and aqueous solutions A and E of Example 1
=i, and the same treatments and operations as in Example 1 were performed. At this time, the temperature of the heat roller was completely changed, and the results shown in Table 2 below were obtained.

From the above conclusion 1+4, it was found that the method of the present invention can effectively suppress changes in i-plane image density against fluctuations in processing temperature. "Also, in the comparative sample, it is not possible to obtain a high maximum density by increasing the fog density, whereas in the present invention, a high cutting height can be achieved without increasing the fog density.
:I found out that what you get is worth it.

Example 3 Fruit! A Material for Example 2? The operation and treatment were carried out in the same manner as in Example 1 except that the heating time was changed as shown in the table below, and the result was kfj+ as shown in Table 3 below.

The results showed that the present invention allows stable images to be obtained despite variations in heating time.

Example 4 Aqueous Solutions A to G Exposure Exposure Path The same operations and treatments as in Example 1 were performed except that dye fixing material 6 was applied instead of applying it to the optical material, and the results were similar to those in Table 1. I got it. However, in samples B-G, each color is C)01~(1,
An increase in the fog density of 02 was observed.

Example 5 The following 1 was deposited on a polyethylene terephthalate film support.
All the layers were coated in the following order to form a light-sensitive resist.

1) (Nzotriazole silver (n in amount of silver, 629/m'
), red-sensitive silver iodobromide (142y/- in amount of #), dye developer compound example 5A (('1.52.9/-), gelatin (4,2511/lr?), in structure W An auxiliary developer represented by (0,11,9/m'), an antifoggant represented by structure '/m''), a compound of the structure Z (0,95 F/m'') and tricresyl phosphate) (0,90 g/l, z) t-containing layer 2) gelatin (L2.!i '/m'') 3) (Nzotriazole silver (0.62g/W in silver amount?
), green-sensitive silver iodobromide (1.14 g/- in silver content)
1 Dye developer compound example (5B) (0,481/rr?)
, gelatin 7 (3,36,!i'/yr?), an auxiliary developer represented by structure W (0°119/d), and an antifoggant represented by structure X (0,20!!/r??). ) layer containing a compound represented by structure Y (o, 3sg/i), a compound represented by structure Z <0.721/n/) and tricresyl phosphate (0°60g/rr?) 4) gelatin <1. sE/n? ') k-containing layer 5) benzotriazole silver (0.45 g/W in silver amount?), blue-sensitive silver iodobromide (0.90 N/R in silver amount), dye developer compound example ( 5G) (o, 2s11/n/>, gelatin (2,8Fl/m"), auxiliary developer of structure W (0,10&/m"), antifoggant of structure X (0,17 , 9/ly/), a compound represented by structure Y (o, 36y/i), a compound represented by structure 2 ('0.80F/m') and hydricresyl phosphate (0,50g/-) 6) Layer A containing gelatin (1,6F/m") Note) (1) Auxiliary developer (Structure W) (21 Antifoggant (Structure X) (31 Compound (Structure Y) 4) Compound (Structure 2) The multilayered color photosensitive material was exposed to 2000 lux for 1 second using a tungsten bulb sound through a three-color separation filter of B, G, and H whose density was continuously changing. The same operations and treatments as in Example 1 were carried out using the dye material of Example 1, aqueous solution A, and Ei.

As a result, the results shown in Table 4 below were obtained.

Table 4 From the above results, it was found that the present invention can increase the maximum fog density without increasing the fog density in all tanks.

Example 6゜ The method of making the emulsion for the first layer will be described.

A well-stirred aqueous gelatin solution (1000 d of water contains 20.9 ml of gelatin and 31 ml of sodium chloride, kept at 75°C), 600 d of an aqueous solution containing sodium chloride and potassium bromide, and an aqueous silver nitrate solution (60,011 t of water).
0.59 mol of silver nitrate dissolved in l) All at the same time 4
Added at equal flow rate over 0 min. In this manner, a monodisperse cubic silver chlorobromide emulsion (80 mol 4 of bromine) with an average grain size of 035 μm was completely prepared.

After washing with water and desalting, sodium thiosulfate 57I9 and 4-human 1
Chemical sensitization was carried out at 60° C. by adding 20 μl of 0x-6-methyl-t,3aa,7-tetrazaindene. The emulsion yield was 600 F.

Next, I will talk about how to make the emulsion for the third layer.

A well-stirred gelatin aqueous solution (containing gelatin 20 I and sodium chloride 3,9 in 1000 mA of water and keeping it warm at 75°C), an aqueous solution containing sodium chloride and potassium bromide, and a silver nitrate aqueous solution (water 600 mA) '
Silver nitrate (0.59 mol gold dissolved in silver nitrate) and the following dye solution (I) were simultaneously added at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mmol of bromine) having a dye adsorbed thereon with an average grain size of 0.35 .mu.m was prepared.

After washing with water and desalting, sodium thiosulfate 51)il and 4-hydroxy-6-methyl-L33a, 7-titrazainde/
Chemical sensitization was carried out at 60°C by adding 20μ. The yield of emulsion was 6001.

Dye solution CI) Methanol 400 Shoulder The method of preparing the silver halide emulsion for the first and fifth layers will be described.

Add 1000ml of an aqueous solution containing potassium iodide and potassium bromide to a well-stirred aqueous gelatin solution (20g of gelatin and ammonia dissolved in 1000d of water and keep warm at 50°C) and an aqueous solution of silver nitrate (1000ml of water). 1 mole of silver nitrate) and pAg k
It was added while keeping it constant. In this manner, a monodisperse silver iodobromide octahedral emulsion (5 moles of iodine) with an average grain size of 0.5 μm was completely prepared.

After washing with water and desalting, chloroauric acid (tetrahydrate) 5■ and thiosulfuric acid)
Gold and sulfur sensitization was carried out at 60° C. with the addition of 2 μm of IJ. The yield of emulsion was 1.0 kg.

Note that the Bensito IJ azole silver emulsion and the gelatin dispersion of the dye-providing substance were prepared in the same manner as in Example 1.

Using these materials, a color photosensitive material with a multilayer structure as shown in the following table was made.

Using a tungsten light bulb, the multilayered color photosensitive material was exposed to light at 2000 lux for 1 second through a three-color separation filter of B, G, and R whose density was continuously changed.

The aqueous solution A of Example 1 was applied to the emulsion surface of this exposed light-sensitive material.
, Ei were fed together using a wire bar of 20 ad/m"k, and then the dye fixing material of Example 10 was used and superimposed so that the membrane surfaces were in contact. Thereafter, the same treatments and operations as in Example 1 were carried out, and the following table was obtained. -5 result was obtained.

The above table shows that the dye images obtained by the method of the present invention have better image quality than those obtained by the comparative method.

(Effects of the Invention) By using this method, it is possible to easily obtain stable and clear images with little fog even when the developing conditions vary.

Claims (1)

[Scope of Claims] 1) A light-sensitive material containing at least a light-sensitive silver halide, a binder, and a dye-providing substance is coated on a support with water, a base, and/or a base precursor, after or simultaneously with the imagewise exposure. and an imaging method comprising heating in the presence of at least one antifoggant to form an imagewise distribution of mobile dye. 2) The image forming method according to claim 1, wherein the antifoggant is contained in the water.