JPS59180550A - Image forming method - Google Patents

Abstract

PURPOSE:To form a polychromatic dye image by heating in a state in which water is not practically contained by using a multilayered photosensitive material contg. dye providing substances which release hydrophilic yellow, magenta and cyan dyes, respectively by heating. CONSTITUTION:A multilayered photosensitive material having at least three silver halide emulsion layers which are sensitive in different spectral regions and nonphotosensitive hydrophilic colloidal layers adjacent to the emulsion layers on a support is heated in a state in which water is not practically contained during or after imagewise exposure. The colloidal layers contain dye providing substances which have power of reducing photosensitive silver halide and release hydrophilic yellow, magenta and cyan dyes, respectively by a reaction with the silver halide under heating. Said movable hydrophilic dyes released by heating the photosensitive material are transferred to a dye fixing layer to obtain a polychromatic dye image.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a new method for forming multicolor dye images by heating in substantially water-free conditions.

The present invention particularly relates to a new method of transferring dye released from a heated trap to a dye fixing layer to obtain a multicolor dye image.

In the present invention, multicolor means a range of colors that can be reproduced using the three primary colors of subtractive color mixture. For color reproduction using the three primary colors of subtractive color mixing, please refer to “The Theoryofth”
ePhotographicProc'ess"tlt
hEd. (Edited by T.H.James's)!
; 677 pages from A/member and the new color science handbook (
(edited by the Color Society of Japan, University of Tokyo Press).

Many methods have been proposed for obtaining a color image (Rikinoichi image) using a dry method. Regarding a method of forming a color image by combining an oxidized form of a developer and a coupler, U.S. Pat. 3.7t/. ，! In 70', p-amine phenolic reducing agents are described in Belgian Patent No. 10J', No./P and Research Disclosure/T.
'February issue 3/. ．． On page 32, sulfonamide phenolic reducing agents are also described in U.S. Pat.
No. 110 proposes a combination of sulfonamidophenol reducing agent 4 and an ≠equivalence coupler.

However, this method has the disadvantage that a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a cloudy color image. To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer, but it is necessary to distinguish between the unreacted material and the dye. It has the disadvantage that it is not easy to transfer only the dye.

In addition, a method of introducing a nitrogen-containing heterologous group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure magazine Lta 7lr 2015/J issue tp~jg Page D-/4 ta. Described in AA. With this method, it is difficult to suppress the release of dye in areas that are not exposed to light, and a clear image cannot be obtained, so it is not a common method.

Regarding the method of forming positive color images by thermal silver dye bleaching method, for example, see pages 30 to 32 of Research Disclosure magazine/Ta, January 1976 issue (■ also D-/φ
≠33), same magazine/TA, February 1976 issue/≠~/! Bage (RD-/.tλ'λ7), US Patent No. ≠, 23! , Taj No. 7, etc., describe useful dyes and bleaching methods.

However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting color images may not coexist during long-term storage. It had the disadvantage of being gradually reductively bleached by free silver.

Further, regarding the method of forming color images using leuco dyes, for example, U.S. Pat. No. tj, No. φ
．． 02λ, z/7. However, this method has the disadvantage that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage.

Furthermore, the above-mentioned methods generally require relatively long periods of time for development, and the resulting images have the drawbacks of high fog and low density.

The present invention provides a new method for forming heated multicolor dye images in a substantially water-free state,
Moreover, it solves the drawbacks of conventionally known materials.

That is, the object of the present invention is to provide a material containing substantially water. The present invention provides a new image forming method in which a mobile hydrophilic dye released by heating is transferred to a dye fixing layer in a non-active state to obtain a multicolored color image.

The object of the present invention is to react with photosensitive silver halide in a substantially water-free state by heating to produce a mobile yellow
The object of the present invention is to provide a new multicolor photographic material containing a dye-donating substance that releases magenta and cyan dyes.

An object of the present invention is to provide a method for obtaining a clear multicolor image using a simple method.

These purposes include having at least three silver halide emulsion layers sensitive to different spectral regions on a support;
Each emulsion layer or a non-light-sensitive hydrophilic colloid layer adjacent to each emulsion layer has a reducing property for light-sensitive silver halide, and when heated, it reacts with light-sensitive silver halide to produce a yellow color. Simultaneously with or after imagewise exposure, a multilayered light-sensitive material containing a dye-donating substance that releases hydrophilic dyes, magenta and cyan, respectively, is heated in a substantially water-free state. , is achieved by a method of imagewise formation of mobile dyes.

In the single image forming method of the present invention, a silver image and a movable dye can be simultaneously applied to the area corresponding to the silver image by simply heating at the same time as or after image exposure. That is,
In the color image forming method of the present invention, imagewise exposure is carried out, and heat development is performed in a state substantially free of water, whereby the exposed photosensitive silver halide is used as a catalyst to form a photosensitive silver halide and a reducing dye-donating substance. A redox reaction occurs between the two, producing a silver image in the exposed area. In this step, the dye-donating substance is
It is oxidized by silver halide to form an oxidant, υ, and as a result, a hydrophilic mobile dye is released, and in the exposed area, a silver image and a mobile dye are obtained. At this time, the presence of a dye release aid accelerates the above reaction. A dye image is obtained by moving this mobile dye to, for example, a dye fixing layer.

The above is a case where a negative type emulsion is used, but when an autopositive emulsion is used, the process is the same as when a negative type emulsion is used, except that a silver image and mobile dye are obtained in the unexposed areas. .

The oxidation-reduction reaction between the photosensitive silver halide and the dye-donating substance of the present invention and the subsequent dye-releasing reaction are characterized in that they occur at high temperatures and in a dry state that does not substantially contain water. . Here, "high temperature" refers to a temperature condition of 10"C or higher, and a dry state that does not substantially contain water refers to a state in which the moisture in the air is in equilibrium, but there is no water supply from outside the system. Say, 'The Theor' in such a state.
yofthePhotographicProcess
”xitbEd, (EditedbyT.H, James
s, Macmillan), page 37+.

The fact that a sufficient reaction rate is exhibited even in a dry state substantially free of water can be confirmed from the fact that the reaction rate of the sample vacuum-dried at 0-3 mηzHg/day did not decrease.

Conventionally, the dye release reaction is thought to be caused by attack by a so-called nucleophile, and is usually carried out in a liquid with a high pH of pH/0 or higher. However, it is unexpected that the present invention does not show a high reaction rate at high temperatures and in a dry state substantially free of water. Moreover, the dye-donating substance of the present invention can be used without the aid of a so-called auxiliary developer.
Can perform redox reactions with silver halide. This is an unexpected result based on previous knowledge of wet development at temperatures around room temperature.

The above reaction proceeds particularly well in the presence of an organic silver salt oxidizing agent, resulting in high image density. Therefore, it is a particularly preferred embodiment to coexist with an organic silver salt oxidizing agent. As mentioned above, the three subtractive color mixtures of yellow, magenta, and cyan
In order to obtain a wide range of colors in the chromaticity diagram using primary colors, the light-sensitive material used in the present invention must have at least three silver halide emulsion layers each sensitive to a different spectral region. .

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include a combination of a light-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer; a green-sensitive emulsion layer; A combination of a sensitive emulsion layer and an infrared sensitive emulsion layer, a combination of a stomach sensitive emulsion layer, a green sensitive emulsion layer and an infrared sensitive emulsion layer, a blue sensitive emulsion layer, a red sensitive emulsion layer and an infrared sensitive emulsion layer. There are combinations of emulsion layers. Note that here, the infrared light-sensitive emulsion layer is 700 nm or more,
In particular, it refers to an emulsion layer that is sensitive to light of 74 LOHm or more.

The light-sensitive material used in the present invention may have an emulsion sensitive to the same spectral region divided into two or more layers depending on the sensitivity of the emulsion, if necessary.

Each of the above emulsion layers and/or the non-photosensitive hydrophilic cowide layer adjacent to each emulsion layer contains a dye-donating substance that releases a yellow hydrophilic dye and a dye-donating substance that releases a magenta hydrophilic dye. and a dye-donating substance/species that releases a hydrophilic dye of cyan.

In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain dye-donating substances that release hydrophilic dyes of different hues. If desired, it is also possible to use a mixture of λ or more dye-providing substances having the same hue.

Figures 1 to 1 show typical layer structures of the sensitive material used in the present invention. Figure 1 shows a red-sensitive emulsion layer RL (C) containing a cyan dye-providing substance on a support S, an intermediate layer IL, an edge-sensitive emulsion layer GL ([4) containing a magenta dye-providing substance, and an intermediate layer]. It shows a layer structure in which IL, a blue-sensitive emulsion layer BL(Y) containing a yellow dye-donating substance, and a protective layer PC are provided in this order. Since the yellow dye-donating substance contained in BL(Y) itself exhibits yellow coloration, the yellow filter 1-
However, if the dye-donating substance itself is insufficiently yellow, BL and GL are omitted as shown in Figure λ.
Colloidal silver, yellow dye, or the like may be contained in the intermediate layer between the layers, and this intermediate layer may be used as a yellow filter layer YF. Figure 3 shows OLCM) and RJL (of the layer groove configurations in Figure 3).
This shows the layer structure in which the order of C) is reversed.

FIG. )
, an intermediate layer IL, a green-sensitive emulsion layer GL(Y) containing a yellow dye-donating substance, and a protective layer PC are shown in this order.

The second figure shows an infrared light-sensitive emulsion that contains a magenta dye-donating substance by replacing the dye-providing substances contained in the infrared-sensitive emulsion layer and the red-sensitive emulsion layer in the layer structure shown in figure q. This shows a layer structure in which red-sensitive emulsion layers R, L (C) containing a cyan dye-providing substance are provided on layers IR, T, (M) via an intermediate layer (L). Figure 6 shows I, L (M) and R in Figure 5,
This shows a layer structure in which the order of L (C) is reversed. FIG. 7 shows a layer structure in which an antihalation/mAHL and an intermediate layer L are provided between In, L(C) and the support S as shown in the layer structure of FIG.

FIG. Non-photosensitive layer CL containing a substance, red-sensitive emulsion layer RL, intermediate layer IL
, a non-photosensitive layer ML containing a maze/ta dye-donating proboscis, a green-sensitive emulsion layer GL, an intermediate layer (1), a non-photosensitive layer YL containing a yellow dye-donating proboscis. ．． A night-sensitive emulsion layer BL and a protection r@pc are provided.

Figure 1 is in Figure 10B. L(Y) and R,I,(C
) shows the demographic structure that has been achieved.

The layer configurations shown in Figures 1 to 3 are suitable for applying exposure from the conspiracy layer PC side, but if the support S is transparent, exposure can be applied from the support S side. good. However, the layer structure shown in Figure 3 is most suitable for applying light exposure from the support S side.

The structure having each color-sensitive emulsion layer of IRLXRL and (}L shown in FIGS.
This is an example suitable for applying intensity-modulated or on-off modulated exposure to a light source such as a semiconductor laser or a semiconductor laser using a light signal.

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

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.

Sensitizing dyes useful for this purpose generally include merocyanine dyes, cyanine dyes, oquinol dyes, and specifically T. H. "The 'J'" edited by James
heoryofthePi1otographicpr
4-2311, German Patent No. 92, OGO, US 1, 3,
No. 7171, 2,303.77/l, issue, same, evening/
ta, ooi issue, same. 2.9'/. 2, 3,! Ta, No. 3
, &j [, Tata No. 3, I! l7.2, 1ta No. 7,
3, lr94t, 2/7, 4'. 02 evening, 311
? No., same≠,0≠6, E72, British Patent/,2gλ,
J and G, special public show≠17-/≠030, same evening 2-1ψ
li”7≠ issue, and those described in Japanese Patent Application Laid-open No. 3-/≠q727.

Specific examples of sensitizing dyes useful in the present invention include the following general formulas (Δ) to (H.), (J) to (U), (W), (Y
).

General formula (A) In the formula, Z1 and Z2 are heteroclonal nuclei usually used in pacyanine dyes, especially thiazole nucleus, thiapurine nucleus, penzothiazole nucleus, naphthothiazole nucleus, mexazole nucleus, oxazoline nucleus, penzoxazole nucleus, naphthothiazole nucleus, Zazole nucleus, tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidazoline nucleus, imidazole nucleus, penzimidazole nucleus, naphthoimidazole nucleus, selenazoline nucleus, selenazole nucleus, penzoselenazole nucleus, naphthoselenazole nucleus, or indolenine nucleus, etc. represents the atomic group necessary to complete the . These nuclei include lower alkyl groups such as methyl groups, halogen atoms, phenyl groups, hydroxyl groups, carbon numbers/
Substituted with an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylsulfamoyl group, an alkylcarpamoyl group, an acetyl group, an acetokizo group, an ano group, a trichloromethyl group, a tri7fluoromethyl group, a nitro group, etc. It's okay.

L1t or L2 represents a methine group or a substituted methine group. Examples of substituted methine groups include methine groups substituted with lower alkyl groups such as methyl group and enal group, phenyl group, substituted phenyl group, methoxy group, and ethoxy group.

Ft and 1{2 are alkyl groups with a carbon number of / to O; substituted alkyl groups having a carboxyl group; γ-sulfopropyl group, δ-sulfobutyl hs, -z-(J-sulfopropoxy)ethyl group, λ- (.2-(3-sulfopropoxy)
[ethoxy] ethyl group, 2-hydroxy sulfopyl group, and sulfo group-substituted alkyl group; allyl (al
lyl) group and other substituted argyl groups commonly used as N-substituents of cyani/dyes. Il1? Pa/
, 2 or 3. X0- represents an acid anion group such as iodide ion, bromide ion, p-toluenesulfonate ion, perchlorate ion, etc., which is commonly used in anionic color formation. npa/tta (dyu), and when taking the betaine structure, n is /.

General formula CB) In the formula, Z3 is the general formula (A
) represents a more heterocyclic nucleus.

Z4 represents an atomic group necessary to form a ketohetero nucleus commonly used in melonanine dyes.

Examples include rhodanine, boohydantoin, oxindole, 2-thioxazolidinedione, /,3-indanedione, and the like. L3 and L4 have the same meaning as L1 and L2, and R3 has the same meaning as R1 or R2. m2pa/, λ, represents 3-matapa≠.

General formula (C) In philtrum, Z5 is ≠-quinoline nucleus, 1 to quinoline nucleus, benzthiazole nucleus, benzselenazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, naphthoxazole nucleus,
The atomic groups necessary to complete the penzoselenazole nucleus and indolenine nucleus are shown.

p1 represents/or ko.几, is R e or R2 and 16
1. Regi, L5 and L6 represent the same meaning as L3 or L4. 1]]3 represents l or 2. L7 and L8 are L
It has the same meaning as D or L2. Z6 represents the same meaning as Z4. Y and Y2 are an oxygen atom, a sulfur atom, a selenium atom, or =N-It5 (R5 an alkyl group with a carbon number of g or less, such as a paminetinol, ethyl, and proyl group, allyl
! ) represents a group), at least one of which is =N-R
There are 5 units. W1 is l or . Represents 2.

1-General formula CD) In the formula, Z7 is Z5 and Z8 is Z6 and R, Id. R, or 几2 and p2 represent the same meaning as W. Are Y3 and Y4 Y? and Y
It has the same meaning as 2. w2 has the same meaning as w1.

In the formula, RJ7 and RJ8 are 几, or R2, Z, and Zio
Or Z5 and p3 and p4 are W, L9 to L13 are L1 or L2, and X2 is X? and n2 represent the same meaning as ne.

Y5 and Y6 have the same meaning as Y0 and Y2. p5,m
4 is. Father represents /. w3 has the same meaning as w1.

General formula (F) In the formula, 2? , and Z1? is unsubstituted, or especially a lower alkyl group such as a methyl group, a halogen atom, a phenyl group,
Hydroxyl a, R element ta' to Hiro's alkoxyl group, carboxyl group, alkoxycarbonyl group, alkylsulfamoyl group, alkylcarpamoyl group, acetyl group,
Represents the atomic group necessary to complete a benzene ring substituted with a cyano group, trichloromethyl group, nitro group, etc., or the atomic group necessary to form a naphthyl ring. R, and R1o represent the same meaning as R or R2. Y7 and Y8 are oxygen atoms, sulfur atoms, selenium atoms, (R, FLE2 are methyl groups or ethyl groups), 2N11 (1? is an alkyl group, usually an N-substituent of cyanine dyes) (represents a substituted alkyl group or allyl group used for) or -CH=CH
represents one. Y9 is! Or represents a group of atoms necessary to form a two-membered heterocycle.

General formula CG) Z? 3. Z14r, Ze? Or Z1? What R? 2 and 1 also
3 is R? Or R2 and "10", 11, Y7, and ¥8 represent the same meaning. Y42i disciple. T or member carbon j! Represents the atomic group necessary to form J. X3 is X1 and n3 is n1
expresses the same meaning as

General formula (H) General formula (J) X4 represents the same meaning as X1. m4, m5 are/or 2,
L1? ~L. represents the same meaning as L1 or L2. 2e, is Z? Or it has the same meaning as Z2.

Here, A? as, “S, to J”” ゛゜Supplement 6 ρ１′゛ NO2 Also, as A2, 11: Ji...8 eyu ■NIt18 5 ”16 20～ I would like to get Q 0/゛1 It can be mentioned as one of the following.

R16 represents a water atom, an alkyl group, a substituted 14 alkyl group, or an aryl group. Rin? 5 is a nitrogen atom, a nitro group, a lower alkyl group, an alkoxy group, an alkoxy carbonyl group, an alkylsulfonyl group, an arylsulfonyl group - + Table br. R1. , 1t08, R.
Q represents rhodanine, λ-
Represents the atomic group necessary to complete the r-4, membered complex nucleus of thioxazolidinedione, nothiohydantoin, barbituric acid, etc.

General formula (K) Is R20 R? Or 几2 and Z16 are Z1 and L? 6. L?
7 represents the same meaning as L1 or L2. p7 represents 0 or /, and p8 represents /, 2 or 3.

G1 and G2 may be the same or different;
For example, pyrrolidone, 3-pyro+)7, piverizinene, piperazine, morpholine, /,2,3,gutetrahydroquinolinol/, decahydroquinoline, 3-azabicic mouth C3
、． 2,. 2) Represents the atomic group necessary to form nonane, indoline, azetine, and hexahydroazepi/). X5PX1 and n5 represent the same meaning as n1.

General formula (L) Z is z4 and L18’”19, L20 is L117 Father represents L2 and G3, and G4 represents the same meaning as G1 and G2.

p9 represents 0, /, λ or 3.

Particularly useful dyes for imparting infrared sensitivity are dyes represented by the following general formulas (M) to (U), (W), and (Y).

General formula (M) Here, R1 and R2 may be the same or different, and each is an alkyl group (number of carbon atoms/~
g5 For example, methyl group, ethyl group, probyl group, butyl group, bentyl group, heptyl group, etc.), substituted alkyl group {
Examples of substituents include a carboxy group, a sulfo group, an ano group, a fluorine atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxy group, an alkoxycarbonyl group (a carbon atom number of ♂ or less, e.g. methoxy carbonyl group,
(Ethoxycarbonyl group, Penzyloxy 7-carbonyl group, etc.), Alkoxy group (7 or less carbon atoms, e.g. methoxy group, Ethoxy 7 group, Propoquine group, Butoxy group, Penzyloxy group, etc.), Aryloxy group (e.g. Phenoxy group) , p-tolyloxy group, etc.), acyloxy group (up to 3 carbon atoms, e.g. acetyloxy group, propionyloxy group, etc.), acyl group (up to 3 carbon atoms,
(e.g. acetyl group, propionyl group, benzoyl group, menyl group), carbamoyl group (e.g. carbamoyl group, N,N-dimethyl group, morpholinocarbamoyl group, piveridino group), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.),
An alkyl group (having 6 or more carbon atoms) substituted with an aryl group (for example, a phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, α-naphthyl group, etc.). However, two or more of these substituents may be substituted into an argyl group in combination. } represents.

In the general formula (M), ¥1 and ¥2 are oxygen atoms, sulfur atoms, selenium atoms, (几., R4 is a methyl group or an ethyl group), =N-R5
(R5 is an unsubstituted or substituted alkyl group with a carbon number of 0 or less (common substituents include a hydroxyl group, a halogen atom, a carboxyl group, a sulfo group, an alkoxy group, etc.) or an allyl group] or one CH=CH - represents.

Z in general formula (M)? , Z2 represents an atomic group essential to form an unsubstituted or substituted benzene ring or naphthyl term. Examples of substituents include lower alkyl groups such as methyl groups, halogen atoms, phenyl groups, hydroxyl groups, alkoxy groups having 1 to 3 carbon atoms, carboxyl groups, alkoxy-rubonyl groups, alkylsulfamoyl groups, and alkyl-rubamoyl groups. , acyl group, cyan group, trifluoromethyl group, nitro group, etc.

Nitrogen-containing complex tombs made of Y1 to Z1 and Y2 to Z2 include, for example, thiazole core systems [e.g., penzothiazole, Koichi chlorobenzothiazole, j-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, ≠-Methylbenzothiazole,! -Methylbenzothiazole, t-methylbenzothiazole, t-methylbenzothiazole, mobenzobuazole, promobenzothiazole,! - Iothhenzothiazole, j-phenylbenzothiazole, j-methoxypenzothiazole, 2-methquinepenzothiazole, 5-ethoxybenzothiazol, tercarboxyzobenzothiazole, monoethoxylponylbenzothiazole , j-phenethylbenzothiazole, trifluoropensothiazole, j-trifluoromethylbenzothiazole, ! , Otsuichi dimethylbenzothiazole, E-hydroxy-A-methylbenzothiazole, tetrahydride-penzothiazole, V-phenylbenzothiazole, Na7}(-z,/-d)thiazole,
Naft [/,. 2-d) Thiazole, naphtho[no,3-
rl) Guazole, j-methoxynaf} (/,.2-
d) Thiazole, 7-ethquinnaphtho[λ,/-d)thiazole, do-methoxynaphtho(,!,/-d)thiazole,! -methoxy7naphtho(J,J-d)thiazole, etc.], selenazole nuclear systems (e.g., hapenzoselenazole,
Oak mouth rubenzozelenazole core, j-methoxybenzozelenazole,! -methylbenzozelenazole, j-hydroquine benzoselenazole, napf l-(j,/-d)
zelenazole, naphtho(/.2-d) zelenanol, etc.], oquinazole nuclear systems [e.g., penzoxazole, j-chlorobenzoxazole, methylbenzogisazole, brolbenzoxazole, j- fluorobenzoxazole, orphenylbenzoxazole, s-methoxyhenzoxazole, J-to 1) fluorobenzoxazole, j-hydroxybenzoxazole, j-carpoxybenzoxazole, t-methylbenzoxazole, t-chlorobenzoxazole, Otsuichi methoxybenzoxazole, 2-hydroxybenzoxazole, 3゛,l-dimethylbenzoxazole-7v, 'l*A-dimethylbenzoxazole,
Yoichi Etoki/Penzoxazole, Naphtho (.2,/-
, 1] oxazole, Nantes (/, .2-(1:) oxazole, Nantes [1.3-d) oxazole, etc.],
Quinoline nucleus [e.g. 2-quinoline, 3-methyl-2-quinoline,! -Ethyl-coquinoline, O-methyl-1-
Quinoline, g-fluoro-λ-quinoline, 2-methquine-λ-quinoline, t-hydroxy-l-quinoline, r-
chlorochoquinoline, zafluoro<2-quinoline etc.], 3,3-dialkylindolenine nucleus (e.g.
3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-! -cyanoindoleni7
, 3.3-dimethyl-j-methoxyindolenine, 3,
3-dimethyl-! -Methylindolenine, 3,3-dimethyl-! -chlorindolenine, etc.), imidazole nuclei (e.g., l-methylbenzimidazole, /1-ethylbenzimidazole, /-methyl-terchlorbenzimidazole, /1-ethyl-!-chlorobenzimidazole, /-methyl-3- , l-dichlorobenzimitazole, /monoethyl-jlz-dichlorbenzimidazole, /-alkyl-j-methoxy/penzimidazole,
/-Methyl! -cyanobenzimidazole, /monoethyl-! -cyanobenzimidazole, /-methyl-fluorobenzimidazole, /monoethyl-! -fluorobenzimidazole, /-phenyluo,2-dichlorobenzimidazole, /-aryruo j. t-Dichlorobenzimidazole, /-aryl-j-chlorobenzimidazole, /-phenylbenzimidazole, /-phenyltachlorbenzimidazole, /-methyl! (1-trifluoromethylbenzimidazole, /1ethyl-1trifluoromethylbenzimidazole, /1ethylnaphtho(/,.2-d)imidazole, etc.).

In the general formula CM), Y3 is! Represents the atomic group necessary to form a member or member carbon ring.

In the general formula CM), m represents l or 2, X1 represents an acid residue.

m2 represents θ″if. or/, and is O when the dye has a betaine structure.

L? , L2 represents a methine group or a substituted methine group. Examples of substituted methyl groups include lower alkyl groups with carbon numbers/~j, lower alkoxy groups, and ryol groups (this aryl group includes
rogene atom, alkyl group with 7-≠ carbon atoms, l-φ carbon atoms
may be substituted with an alkoxy group, a sulfo group, a carboxy group, etc.), a methy/group substituted with an aralkyl group (such as a benzyl group), etc.

General formula (N) In the formula, YY has the same meaning as Y1 and ¥2, and 3\4 R is R? , has the same meaning as R2, and 617 z3, Z4HZ? , Z2 has the same meaning as f6, and X2 is X? m3 has the same meaning as m2.

(Here, the same meaning means the same meaning as the definition of general formula (M)) General formula (0) In the formula, Z5 is an atom necessary to form a ≠-quinoline nucleus or a λ-quinoline nucleus. represents a group.

z6 has the same meaning as z1 and z2.

p represents O or /.

m4 represents λ or 3.

Y5 has the same meaning as Y1 and Y2, and R8 and R9 are R? -,, - has the same meaning as R2, 9, X3 has the same meaning as X1, m5 has the same meaning as m2, and L3 and L4 have the same meaning as L? , has the same meaning as L2.

(Here, "dogi" means the same meaning as the foot prosthesis of the general formula CM)) General formula (P) In the formula, ZB%ZgId. I like Z1 and Z2! So, ordinary.

, R01 is R? , has the same meaning as R2, Y8 has the same meaning as Y3, and X4 has the same meaning as X? m6 has the same meaning as In2, and Y6, Y7FiY,, Y2 has the same meaning.

(Here, the same meaning means the same meaning as the definition of general formula CM). represents an alkyl group having carbon number/~t or a phenyl group.

General formula (Q) During the ceremony, Z? . has the same meaning as Z1 and z2, Y9 has the same meaning as YE and Y2.

￥11ll'i Oxygen atom, sulfur atom, selenium atom, =N
-R,? 6 (几?6t.J: Same meaning as 几.).

R? It has the same meaning as 4parR1 and 几2.

R? 5 represents R, a group having the same meaning as R2, a phenyl group, and a pyridyl group.

Y? . has the same meaning as Y3, Is m7 an m? It has the same meaning as L5 and L6 have the same meaning as Le and L2.

(Here, the same meaning means the same definition as the fixed value of the general formula (M)) General formula (R) In the formula, Z,'YYXY,R,,R, 109'10111415 and m7 are the general formula It has the same meaning as (Q).

During the ceremony, Z? 1.Z? 2 is Z? , has the same meaning as Z2, Y12,
Y14 has the same meaning as Y,, Y2, and R17, R,? 9
has the same meaning as R1 and R2.

2'L18 represents a lower alkyl group or an allyl group having t or less carbon atoms.

"13i'j:" has the same meaning as 3, X5 has the same meaning as X1, m7 has the same meaning as m2.

(Here, the same meaning means the same meaning as the foot allowance of general formula (M)) In the formula, Z13 and Z14 have the same meaning as Z1 and Z2, and Y? 5,
Y16 pa Y? , has the same meaning as ¥2, R1?1, 几. ?
has the same meaning as R1, R, 2, X6 has the same meaning as Xe, and m8 has the same meaning as m2.

(In the above, the same meaning means the same meaning as the definition of general formula (M)) 1t2o has the same meaning as R18 of general formula (S).

During the ceremony, ¥1? has the same meaning as Y3, Y? 8 is the same as Y1 and ¥2, Z? 5 has the same meaning as Z5, Z has the same meaning as z1 and z2, 16 R, R2, l-j: R? , has the same meaning as R2, and 23 q has the same meaning as p, X7 has the same meaning as X1, m9 has the same meaning as m2.

(In the above, the same meaning means that it has the same meaning as the definition of general formula CM). R25, is R in general formula (S). It has the same meaning as

During the ceremony, Z1? , z18 has the same meaning as Z1 and Z2, Y,9,
Y2oI/iY? , Same meaning as Y2, R26, 几.

? ke has the same meaning as R, 1, and R2, X8 has the same meaning as X4, m1o has the same meaning as m2, and L7 has the same meaning as L? , has the same meaning as L2.

(In the above, the same meaning means the same meaning as the definition of general formula (M)) "28" has the same meaning as "18" of general formula (S).

In the formula, Z19 and Z2o have the same meaning as Zi and Z2, and Y2? ,
Y22 has the same meaning as Y1 and Y2, and R2, 几. . is the same as 几,,R2,LLLXL%L12,L1
3, 8\9~1011 L14 has the same meaning as L0 and L2, X9 has the same meaning as X1, m? 1 has the same meaning as m2.

(Here, the same meaning means the same meaning as the definition of the general formula CM). Specific examples of the sensitized color composition used in the present invention are shown below. The sensitizing dye used in the present invention is not limited to this.

-397- -398- -399- Itton Loss 1-401-402-403 404-These sensitizing dyes may be used alone or in combination. Combinations of sensitizing colors are often used, especially for the purpose of supersensitization. A typical example is the US patent λ,2♂t,jt4t! No. 2, ? No. 77,229,
3.397.010, 3, Tayuko, Oj2, 3. j;27. A≠/No. 3, t/7, 293, No. 3, A. :lg. 91, 'i No. 3. ttt, 710
No. 3, t7.2, r No. j, <7P, g.
2t issue, same J, 703,? No. 77, 3, Za/lI. ，
t09, 3, r37, Zaotsu λ, 1, p, Oxl,,
No. 707, British Patent/,3≠g,2za/No., same/,30
No. 7,103, Special Public Show 13-≠23t No. 13-/2
, No. 37j, JP-A-Shoz. z-iio, ti. r number, same j
21 iota, ta. It is described in No. 2j.

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 be included in the entire emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heteroclonal groups (for example, U.S. Pat.
71/), aromatic organic acid formaldehyde condensates (for example, US Pat. No. 3,7≠3.J;/0
(described in the above issue), cadmium salts, azaindene compounds, etc. U.S. Patent 3,z/o, 673;
The combinations described in No. 3, 4/j, Otsu≠/, No. 3, 6/7, No. 2, No. 3, t3, and No. 727 are particularly useful.

In order to incorporate these sensitizing dyes into silver halogenide photographic emulsions, they may be directly dispersed in the emulsion, or they may be dispersed in a single solvent such as water, methanol, ethanol, acetone, or methyl cellosolve. Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Alternatively, after dissolving them in a substantially water-immiscible solvent such as 7-enoxyethanol, they may be dispersed in water or a hydrophilic colloid, and this dispersion may be added to the emulsion. Furthermore, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. Further, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately, or a mixture may be dissolved. Also, when added to an emulsion, it may be added at the same time as a mixture, or
It may be added separately or simultaneously with other additives. It may be added to the emulsion at the time of chemical ripening or before or after chemical ripening.

The amount added is generally about 9/θ-8 to 0-2 mol per 7.silver halide/mol.

Silver halides used in the present invention include silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide.

In the present invention, without using an organic silver salt oxidizing agent...
When silver halide is used alone, particularly preferred silver halide is one containing silver iodide crystals in part of its grains. In other words, when X-ray diffraction is performed on silver logenide, the ξtano of pure silver iodide is particularly suitable.

For photographic photosensitive materials. A silver halide containing two or more types of atoms is used, but in a normal halogen arsenic emulsion, the halogen arsenic grains are completely mixed crystal.

For example, when measuring X-ray diffraction of the grains of a silver iodobromide emulsion, no patterns of silver iodide crystals or silver bromide crystals appear, but X-ray nomiturns appear at positions corresponding to the mixing ratio.

Particularly preferred in the present application...Silver rogenoide contains silver iodide crystals in its grains, and therefore silver chloroiodide, silver iodobromide, and silver chloroiodobromide in which the X-rays and miterns of silver iodide crystals appear. be.

In the case of silver iodide, a silver nitrate solution is added to a potassium solution to form silver arsenic particles, and then potassium iodide is added. obtained by.

Two or more types of halocarbons having different sizes and/or halocarbon compositions may be used in combination.

The size of the halogen f arsenic particles used in the present invention preferably has an average particle diameter of 0.00/μm to 70 μm,
More preferably, it is 0.00/μm to jμm.

The halogen used in the present invention may be used in its pure form, but it may also be used in combination with sulfur, selenium, tellurium, etc., gold, platinum, radium, rhodium, iridium, etc.
The sensitizers may be sensitized by the use of chemical sensitizers such as halogen compounds, reduced sensitizers such as halogen compounds, or combinations thereof.
fthoPhotographicProcess”4
'Edition, T. H. It is described in Chapter J/≠Page ~/Ota page of John James.

A particularly preferred embodiment of the present invention is one in which organic silver is simultaneously removed with hydrochloric acid.
When heated to the above temperature, it reacts with the image-forming substance or a reducing agent coexisting with the image-forming substance as required to form a silver image. By coexisting with an organic silver hydrochloride arsenic agent, it is possible to obtain a photosensitive material that develops color at a higher density.

In this case, the arsenic used in the present invention is not necessarily characterized by containing pure iodine silver crystals when used alone, but is known in the art.・You can use all of Roken R's silver.

One soldier. 4G. A'isv, please sing } Hiki A Kake 1 Take 1 self 1 possible S color hawk 7, / Mouth': / 72 N' and the monument 1 A0 I} Me force 5 spine 1 Is it clean? Examples of such organic silver salt oxidizing agents include the following.

It is a silver salt of an organic compound having a carbokylene group, and typical examples include silver salts of aliphatic canoleboic acids and silver salts of aromatic carboxylic acids.

Examples of aliphatic carbonic acids include silver salts of behenic acid, silver salts of stearic acid, silver salts of oleic acid, silver salts of lauric acid,
Capri/Silver salt of acid, Myristi/Silver salt of acid, Silver salt of palmitic acid, Silver salt of maleic acid, Silver salt of fumaric acid, Silver salt of tartaric acid, Silver salt of furinoic acid, Silver salt of linoleic acid, Oleino acid. Examples include silver salts of acids, silver salts of adipic acid, silver salts of sebacic acid, silver salts of succinic acid, silver salts of acetic acid, silver salts of butyric acid, and silver salts of camphoric acid. Also effective are these silver salts substituted with a 7-rogen atom or a hydroxyl group.

Silver salts of aromatic carbo/acids and other carbokylene group-containing compounds include silver salts of benzoic acid, silver salts of 3,j-dihydroxy7benzoic acid, silver salts of 0-methylbenzoic acid,
Substituted benzoic acids such as silver salt of m-methylbenzoic acid, silver salt of p-methylbenzoic acid, silver salt of λ,4'-dichlorobenzoic acid, silver salt of acetamidobenzoic acid, silver salt of p-phenylbenzoic acid, etc. Silver salt of gallic acid, silver salt of tannic acid, silver salt of phthalic acid, silver salt of terephthalic acid, silver salt of salicylic acid, silver salt of phenylacetic acid, silver salt of biromellitic acid, US Patent No. 3 ,7! , and silver salts such as 3-carboxymethyl-≠-methyl-≠-thiazolino-no-thiono described in U.S. Pat. No. 3,330 and Otsu No. 3, silver salts of aliphatic carboxylic acids, etc.

In addition, there are compounds having a mercapto group or a thione group, and silver salts of derivatives thereof.

For example, 3-mercap}-4Z-phenylu/,! , ≠ silver salt of monotriazole, silver salt of 2-mercaptobenozoimidazole, silver salt of eumercapto j-aminothiadiazole,! -Silver salt of Mercazotobe/Notiazole, 2-
(s-ethylglycolamide) silver salt of benozthyanol, S-alkyl (alkyl group with carbon number/~22)
Silver salts of glycolic acids described in JP-A No. 2-2G2.27 such as thioglycolic acetic acid, silver salts of dithiocarboxylic acids such as silver salts of dithiacetic acid, silver salts of thioamides,
Carbokin/-methyl! -Silver salt of phenyl-t-thiopyridine, silver salt of mercaptotriazine, λ~
Silver salt of mercaptobenozoxazole, silver salt of mercaptooxadiazole, silver salt described in the US%84≠, /23, 27 Hiroshi manuscript, for example /,1,≠-Mercap1.
Silver salt of triazole derivative 3-aminoterpendylthio/,2,II-1-riazole, U.S. Pat.
It is a silver salt of a thione compound, such as the silver salt of 3-(.2carboxy/edyl)monk-methyl≠-thiazoli/-2thione described in No. 307, 1, 7g specification.

In addition, there are silver salts of compounds having imino groups. For example, Tokuko Showa 4+4-30270, Dohiroj-/gψ/Otsuko 1
Silver salts of beno-1-lyanol and its derivatives listed in e.g., silver salts of benzo-1-lyazole and alkyl-substituted benzo-1-lyazoles, such as silver salts of pe/zo]-lyazole and silver salts of methylbe/zo-lyazole. , silver salts of halogeno-substituted benzotriazoles, such as silver salts of j-crobenzotriazole, silver salts of car-4-zoimidobenzo}IJ azoles, such as silver salts of butylcarboimidobenzo-1-lyazole, U.S. Pat. l: 7, 2, ≠ -1 described in the specification of No. 20,709
- Silver salts of lyazole and /11-tetrazole, silver salts of carbazole, silver salts of saccharin, silver salts of imidazole and imitazole derivatives, etc.

Organic metal salts such as silver salts and copper stearate, which are described in Research Disclosure Vol. It is a metal salt oxidizing agent.

One or more organic silver hydrochloride ratio agents can be used.

Although the thermal development process during heating in the present invention is not fully clarified, it can be explained as follows.

When a photosensitive dye is irradiated with light, a latent image is formed on the photosensitive silver. Regarding this, T.

H. “The Theory of the” written by James
PhotographicProcess"3rdEd
Itjan's ios page~/t is described on the page.

By heating the photosensitive material, a reducing agent, in the case of the present invention, a dye-donating substance, uses latent image nuclei as a catalyst to reduce silver halide or silver halide and an organic silver salt oxidizing agent to produce silver, itself is oxidized. This oxidized dye-donating substance is cleaved to release the dye.

For information on how to make these silver halides and organic silver salt oxidizing agents and how to mix both, please refer to Research Disclosure/No. 70.29 and JP-A No. 0-3,! Ta. 2g
Tokukai Akihiroter/No. 32≠, Tokukai Akihiro 50-/7.2lt
listed in the number.

In the present invention, the total coating amount of photosensitive silver halide and organic silver salt oxidizing agent is tomg~/OQ/7 in terms of silver.
72 is appropriate.

The photosensitive silver halide and organic silver salt oxidizing agents of the present invention are prepared in the binder described below. A color/dye donating substance is also dispersed in the binder described below.

The binders used in the present invention can be contained alone or in combination. This binder has
Hydrophilic materials can be used. Typical hydrophilic binders are transparent or translucent hydrophilic colloids, such as proteins such as gelatino, gelatin derivatives, and cellulose derivatives, and natural substances such as polysaccharides such as temporo and gum arabic. and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Other synthetic polymeric compounds include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes.

The support used in the present invention is one that can withstand the processing temperatures. Common supports include glass, paper, metal, and their analogs, as well as acetyl cellulose film, cellulose ester film, polyvinyl acetate film, polystyrene film, polycarbonate film, and polyethylene terephthalate film. Norems and their related film or resin materials are included. U.S. Patent 3,634'
, No. 089 and No. 3,725,070 are preferably used.

The reducing dye-donating substance that releases the hydrophilic diffusible dye used in the present invention is represented by the following general formula RaSO2D(I).

Here, R and a represent a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye portion having a hydrophilic group.

Dye-donating substance R, i80. Reducing substrate (Ra
) has a redox potential of 7.2 V with respect to a saturated calomel electrode in polar graph half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte.
The following are preferred. A preferred reducing substrate (Ra
) are the following general formulas (n) to (IX).

Here, Ra , alkoxy represents a group selected from alkyl groups, N-f-substituted carbamoyl groups, N4-substituted sulfamoyl groups, halogen atoms, alkylthio groups, and arylthio groups, and the alkyl and aryl groups in these groups are further alkoxy basis,
Halogen atom, hydroxyl group, cyan group, acyl group, acylamino group, substituted carbamoyl group, substituted sulfamoyl group,
It may be substituted with an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group or a carbo'alkoxy group.

Furthermore, the hydroxyl group and amino group in Ra may be protected with a protecting group that can be regenerated by the action of a nucleophilic reagent.

In a more preferred embodiment of the invention, the reducing substrate I%a
is expressed by the following formula (X).

Here, 0 represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. Ra represents an alkyl group or an aromatic group. n represents an integer from / to 3.

10 X represents an electron-donating substituent when n-=/,
When n-λ or 3, the substituents may be the same or different, and when the substituents are electron-donating groups, the
is an electron-donating group or...logeno atom, and
It may form a condensed ring by itself or may form a ring with ORa.

The combined coal tension of both aa and X -1 is greater than or equal to g.

Among those included in formula (X) of the present invention, in a more preferable embodiment, the reducing substrate Ra is represented by the following formulas (Xa) and (Xb).

Here, (}a represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis.R. and 'O"Ra may be the same or different, and each is an alkyl group, or Ra and R
a may be connected to form a ring.

13 Ra represents a hydrogen atom or an alkyl group, and Ra represents an alkyl group or an aromatic group. X and X may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkyl group,
It represents a halogen/atom, an acylamino group, or an alkylthio group, and furthermore, Ra12 and X or R1a0 and RII3 may be connected (to form a ring).

Here, Oa is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis, Ra is an alkyl or aromatic group, X is a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom,
represents an acylamino group or an alkyldio group, and X2 and R
%0 may be connected to form a ring.

Specific examples included in (X), (Xa), and (Xb) are US4t, Ojyo, 4t1g, JP-A-Shoj Otsu-/2&
4t. No. 2 and J&-/Otsu/No. 30, respectively.

In another more preferred embodiment of the present invention, the reducing substrate (Ra) is represented by the following formula (X()).

(However, the symbols Ga, X, Ra and mouth are synonymous with Ga, X, and Ran in formula (X).) Among those included in (XI) of the present invention, in a more preferred embodiment,
The reducing substrate (Ra) is represented by the following formulas (X[a) to (Xlc).

However, Oa is a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; 21 R. a and Ra may be the same or different and each represents an alkyl group or an aromatic group;
may be combined to form a ring; R is a hydrogen atom,
Alkyl group represents an aromatic group; 24 aa represents an alkyl group or an aromatic group; a%5 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a nitrogen atom, or an acylamino group. Representation: p is 0,/or 2; Ra and Ra may be combined to form a condensed ring.
Ra and PUa may be combined to form a condensed ring; Ra and Ra may be combined to form a condensed ring, and RaXRa, Ra\24 B-a and (Ra)p The total number of carbon atoms is greater than 7.

However, Ga is a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; R3al represents an alkyl group or an aromatic group; R3a
2 represents an alkyl group or an aromatic group; R"a3 represents an alkyl group, an alkoxy group, anolekylthio group, an arylthio group, or an alkyl group; q is 0 and/or λ; Ra and Ra may be combined to form a condensed ring; Rt
1 and RXi may be combined to form a condensed term, or Ra and Ra may be combined to form a condensed ring. And F
The total number of carbon atoms in LaXRa and (Ra)9 is greater than 7.

In the formula, Oa represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; 41 aa represents an alkyl group or an aromatic group; 42 R, a represents an alkyl group, an alkoxy group, an alkylthio group,
represents an arylthio group, a rogen atom, or an acylamino group; r is 0 and/or 2; \
The carbonized atoms (1111a-) in the condensed ring that participate in the bonding to the phenol (or its precursor) mother nucleus constitute one element of the condensed compound. A tertiary carbon atom, and a carbon atom in the hydrocarbon ring (
However, some of the above-mentioned tertiary carbon atoms (excluding the tertiary carbon atoms) may be substituted with oxygen atoms, or the hydrocarbons may have substituents, or further aromatic terms may be condensed. 4142-'゛R+a or Ra and the above T---C group may form a condensation term. However, Ra, CRa) r and %----
'c The total number of carbon atoms in one group is 7 or more.

Specific examples included in the above (X[), (X[a) to ('Xlb) are described in patent application Shoj Otsuichi/Otsu/3/, same evening 71 OtsujO, same day j7-≠0≠3 has been done.

The essential part of formula (In) and formula (IV) is the ♀(sulfonyl)aminophenol moiety.

Specific examples include U8J, Ta2g. 3/2, U.S.T.
x. o7b,. tz de, US PublishedPaL
enLAplicaLionB3j/,ly73, (
JS11,/3. f. Ta29', lJSQ, 25g, /
Examples include reducing substrates disclosed in No. 20, which are also effective as reducing substrates (Ra) of the present invention.

In another more preferred embodiment of the present invention, the reducing substrate (Ra) is represented by the following formula (X[l).

Here, Ballast stands for a diffusion-resistant group.

Ga represents a hydroxyl group or a hydroxyl group precursor.

1 Ga represents an aromatic ring and represents a group forming a naphthalene ring together with a pe/zene ring. n and m are/or l
Represents an integer.

Specific examples included in the above stores are US-ttt, oJ″3,
312.

The reducing substrates of formulas (V), (■), (■) and (IX) are characterized by containing a hetero term, and specific examples include US≠, /tag, . 23rd evening, Tokukai Shoj3 Kazuhiro 17
Examples include those described in 30XTJS≠, 273, 133. Specific examples of the reducing substrate represented by formula (Vl) are described in USA, /≠Ta,za92.

The following properties are required for the reducing substrate Ra.

1. To be rapidly oxidized by silver halide and to efficiently release a diffusible dye for image formation through the action of a dye release aid.

2. The dye-donating substance is diffusible in a hydrophilic or hydrophobic binder, and it is necessary that only the released dye has diffusibility. Therefore, the reducing substrate R must have high hydrophobicity.

3. Excellent stability to heat and dye release aids, and should not release imaging dyes until oxidized.

4. For example, it is easy to synthesize.

Next, preferred specific examples of Ra that satisfy these conditions will be shown. In the examples, NH1 represents a linkage with the dye moiety.

=413 Dyes that can be used as image-forming dyes include azo dyes, azomethino dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinol/dyes, carbonyl dyes, and phthalonani7 dyes. Shown by dye. It should be noted that these dyes can also be used in a multi-color, temporarily shortened form during the development process.

Yellow Mazenotashian In the above formula, Ra to Ra each represent a hydrogen atom, an alkyl group, a /chloroalkyl group, an aralkyl group, an alkyl group,
Aryl group, aryl group, anruamino group, a/
group, zoano group, hydroxyl group, alkylsulfonylamine group, arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, ananoalkyl group, alkoxylponylalkyl group, alkoxyalkyl group, arylox/alkyl group, nitro group, haken, Sulfamoyl group, N-substituted sulfamoyl group, carbamoyl M
, Ntjl-substituted carbamoyl group, a7-/L/oxy/alkyl group, amine group, substituted amino group, alkylthio group,
It represents a substituent selected from arylthio groups, and the alkyl and aryl groups in these substituents further include halogen atoms, hydroxyl groups, ano groups, acyl groups, anrylamino groups, alkoxy groups, carbamoyl groups, and substituent groups. It may be substituted with a rubamoyl group, sulfamoyl x, i-substituted sulfamoyl group, carboxyl group, alkylsulfonylamino group, arylsulfonylamino group or ureido group.

Hydrophilic groups include hydroxyl group, carboxyl group, sulpo group, phosphor/acid group, imide group, hydroxamic acid group, quaternary amonium group, carpamoyl group, substituent rubamoyl group, sulfamoyl group, substituted sulfamoyl group, sulfamoyl group, famoylamine group, substituted sulfamoylamino group, ureido group,
Examples include a substituted ureido group, an alkoxy group, a hydroquine alkoxy group, and an alkoxy alkoxy group.

In the present invention, those whose hydrophilicity can be significantly increased by dissociating protons under basic conditions are particularly preferred, including phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, imide groups, and hydroxamyl groups. It includes an acid group, a (substituted) sulfamoyl group, a (substituted) sulfamoylamino group, and the like.

The characteristics required for image-forming dyes are: /) having a hue suitable for color reproduction; 2) It has a large molecular extinction coefficient, 3) It is stable against light, heat, and the dye release aid and other additives contained in the system, ≠) It is easy to synthesize.
Examples include. Specific examples of suitable image-forming dyes that meet these conditions are shown below. Here H2N-s0
2 represents a binding site with a reducing substrate.

Ye IIow -419- -420- Next, specific examples of preferred dye-donating substances will be shown.

422 423 =424-425-426--427-428--429- In addition to the above specific examples, US11.03! ;,lI. 2r,% Kaisho J-&-
/2tlI. 2, Same J[-/t/30, Same st-/Otsu/
3/, same evening 7-6so, same evening t7-4tO≠3, US3,
921,3/. 2, US4t, 071. ，! f2ta, U
SPublishedpatent Application
onB3 evening/, Otsu 73, US≠, /3 evening, Ta 27, US
≠, / tag, 23! ;', Japanese Patent Publication No. 531≠Otsu 73o, U
8tt-,. 273. Irr, USta, /a5p, 1
? 2, USv, /Hiroshiλ, Zata/, lJs4Z,. 2j1
．． Compounds described in /20 and the like are also effective.

Furthermore, (JS11,0/3,t33,USit,/j
1. ．． t09,USv,iag. ttii, US4',
/tj,917,US<z,/III,tll3,US
'A. /f3,7 eveningjXUS4',-24L Otsu, Hiro/Hiro, US11,21. g, l, 23XTJSII,. 21
1j, 0.2g, Tokukai Shoj Otsu-7/07.2. , 31
,-． 2!737, 36-/3za74'! , J. t
-/3411≠2, same 62-701727, same. r/-
//4t? Dye-donating substances that emit yellow dyes such as those described in jθ are also effective in the present invention. −}: TAUS
3, Ta t/7, lI-7 Otsu, US+, 932, 310,
US3, Ta3/, /l. L≠, USj, Ta32,3za/
,USA,. 26g, Otsu. 2lI. , Us4L,. 2s
s, J- (17 ta, JP-A Shoj Otsu-73057, same
7/0 otsu 01 it-/34tg. TO, 63-11
-04102, 36-3tl04t, J-3-23
121, same O λ1/Ot727, same 33-33/4L2
, Same Tata! Dye-donating substances that release mazenota dyes such as those listed in No. 3329 are also effective in the present invention. Also U
83,yxy. yto. ．． TJSti, o/3. g36
, US3,941.2,917, US4L, . 273.
7or, US<z, /4Lr. tax, US+, /r3
,7jll. ,tJsF,/g7,. f! Hiroshi, USA,
/,4j,231,[JS! ,2'l Otsu,4'//+,
UStI-,B;y,g,! ．． t, Japanese Patent Publication Showa J'4-7/
01,/, same j3-≠7. 23, same evening 2-11? ．． 2
7. Dye-donating substances that release cyan dyes, such as those listed in 3323, are also effective in the present invention.

The dye-donating substance may be used in combination with λ species or more.

In this case, two or more types may be used in combination to express the same colorant, and it is also included when λ or more types are used in combination to express black.

The total amount of dye-donating substances is /Omg/Jgar/jg
/m2, preferably 20
Advantageously, a range of m9/m2 to /OJ/J is used.

Next, a method for synthesizing the dye-donating substance will be described.

Generally, the dye-donating substance of the present invention is obtained by condensing the amino group of the reducing substrate Ra with the chlorosulfonyl group of the image-forming dye.

The amine group of the reducing substrate Ra can be introduced by reduction of nitro, nitrono, or azo groups or ring opening of benonoxazole depending on the type of substrate, and can be used as a free base or as a salt of an inorganic acid. On the other hand, the chlorosulfonyl group in the image-forming dye moiety can be derived from the sulfonic acid or sulfonate salt of the dye by a conventional method, ie, by the action of a chlorinating agent such as oxine phosphorus chloride, pentachloride/tisnyl chloride, or the like.

The condensation reaction between the reducing substrate Ra and the image forming dye part D is as follows:
Generally dimethylformamide, dimethylacetamide,
It can be carried out in an aprotic polar solvent such as dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, etc., in the presence of an organic base such as pyridine, picoli/lutidino, triethylamine, diisopropyl ethylamine, etc., at a temperature of 0 to 0°C. Usually, the desired dye-donating substance can be obtained in extremely good yield.

An example of its synthesis is shown below.

Synthesis example/: Synthesis of O-hydroxy-λ-nodylbenozoxazole! , 4t-dihydro/acetophenone 301g, hydroxylamine/hydrochloride/Otsu</-1, sodium acetate 3
2gg, ethanol/I//(1)00ml-. and water. ! 00111 were mixed and heated to reflux for ≠ hours. Pour the reaction solution into water/0 and take out the precipitated crystals.
Dihydroxy/acetophenone oxime 3/IIg was obtained.

7. Dissolve this Oquinom 30f/ in acetic acid q-oo.
While heating and stirring at 20°C, hydrogen chloride gas was blown in for 2 hours. After cooling, the precipitated crystals were collected and washed with water to obtain Z-hydroquino J-methylbenozoxazole/7y.

Synthesis example. 2: A-Hexadenoruki/one! -Methyl〈Synthesis example of nzoxazole/Otsuichi hydroxy synthesized with /-Nomethylbenzoxazole/♂,og,/-Promohexadecane 3 Otsu. ? Q. Potassium carbonate. 2≠． 0 da, N,N-dimethylformamide/20 go? At 00C≠. ! Stir for i hours. Separate the solids from the reaction solution and pour the P solution into a methanol tank.
Opened in 07Bl. The precipitated crystals were collected and A-hexadecyl oxine-nomethylbe/zooquibuzole+13
-, OQ was obtained.

Synthesis Example 3: Synthesis of 2-acetylamino-j-hexadecyloxy/phenol! Obtained Otsuichi hexadecyl oxazole/-no-methylbenzoxazole///fl, ethanol/300ml
, 33 dihydrochloric acid//07Hl and water jj01Hl are mixed,
The mixture was stirred at ~200C for ≠ hours. After cooling, the precipitated crystals were collected to obtain λ-acetylamino-hekizadecyl quinphenol//39 f4.

Synthesis example ≠:,! -acetylamino≠-1-butyl
-Synthesis of hexate-7-yloxyphenol No-acetylamino-j-hexadecyl-oquinephenol obtained in Synthesis Example 3. 20,Of,
30Ome of toluene was mixed, and Ibuteno was blown into the mixture for j hours while heating and stirring at gθ to 0°C. After removing the solid in the oven, the P solution was concentrated, and 3.0% of n-hexane was added to the residue. !
; When Ogl was added, crystals were precipitated. Coacetylamino≠-L-phthyl-j-hexadenluoquinphenol23. I got an offer.

Synthesis example j:,! -Amino-≠-Synthesis of L-Ptyruta Hexatenoluoquinphenol Coacetylamino obtained in Synthesis Example≠≠-[Monobutyl-j-hexade/luoquinphenol 23.0g, ethanol/20Hi, 3J-% hydrochloric acid Mix 9 Otsu ml and! Stir and reflux for hours. After the reaction solution was cooled, the precipitated crystals were collected to give no-amino-≠-t-butyl-hexadenoluoquinphenol hydrochloride. 23.2g was obtained.

Synthesis example t: ≠1[-zutyl-j-hexade/luoki/1λ1[no(.2-me1-ki/ethoxy)-ternitrobe/xenosulfonylamino] 7 Synthesis of enol Obtained in synthesis example S 2 -amino-ψt-butyl! - Hexadecyloxyphenol hydrochloride Hiroshi. Hiroku and 2-(
(eumethoxyethoxy) 1j ditrobenzenesulfonyl chloride IJ. /gwoN,N-dimethylacetamide (12ml) and pyridine. After adding jηt,
Stirred at 0C/hour for 2j0C. When the reaction solution was poured into diluted hydrochloric acid, oily substance precipitated. Methanol 30 for this oil
When 1 liter was added, it crystallized, so this was collected.

Yield ≠, sg.

Synthesis Example 7: Synthesis of 2-(4-amino-λ-(λ-methoxyethoxy)henzensulfonylamino)-[-butyl-j-hexafyloxyphenol] The compound/Og obtained in Synthesis Example 6 above was dissolved in ethanol. AOyn
/O% palladium-carbon catalyst dissolved in ca. After adding Jf, hydrogen was pressurized to 3.5'kg/cm,
The mixture was stirred at 600C for 6 hours. Next, the catalyst was removed while hot, and when it was allowed to cool, crystals precipitated and were taken out in a furnace.

Yield 7, jf0 Synthesis example r: Synthesis of 3-cyano≠1[≠1(.2-methoxyethoxy/)-ter-sulfophenylazo]-1/-phenylter-pyrazolone Sodium hydroxide. In a solution of i', oy and water θOml, add teramino-λ-(2-methquine ethoxy)benose/sulfonate≠7. Add ≠1 and then add sodium nitrate/3,
．． If! An aqueous solution of (Oml') was added.

Separately, prepare a solution of concentrated hydrochloric acid AOtnl and water≠00ml,
The above solution was added dropwise to this at a temperature below 0C. After that evening 0C
The reaction was completed by stirring for 30 minutes.

Separately, sodium hydroxide/B. Og, 200 ml of water, sodium acetate 33. Of and methanol. 200yrt
Prepare a solution of 3-cyano/-phenyl-pyrazolone 37. Of was added thereto, and the prepared giada solution was added dropwise at 70°C or below. 3θ below lO00 after completion of dropping
After stirring for a minute and then at room temperature for an hour, the precipitated crystals were collected, washed with 200@1 acetone, and air-dried.

yield! ;2, OQm, p, 263~. 2 Otsu J-0C Synthesis Example P: 3-/Koichi Anoh [ψ(2-methoxyethoxy)-terchlorosulfonylphenyl aso)-/-phenylu! Synthesis of -pyrazolo/ 3-Cyano obtained in Synthesis Example g above .2 evening Oyn
l and oxochloride lino! Add N to the mixed solution of Oytrl,
N-dimethylacetamide soynl was added dropwise below SO°C. After dropping, stir for about 1 hour and add ice water/. 01 gradually. The precipitated crystals were separated from the furnace, washed with 100 ql of acetonitrile, and air-dried.

Yield≠Otsu, 71m. p. /I/~/g3°C Synthesis Example lO
Synthesis of monodye-donating substance (1) 1-[S obtained in Synthesis Example 7
-amino, 2-(2-methoxyethoxy)benzenesulfonylamino-ψ-(-phthalate hexadecyloxyphenol A. 3fon, N-dimethylacetamide 30ml was dissolved in 30ml of the 3-aminoanol obtained in Synthesis Example 2). ≠1 [≠1 (2-methoxyethoxy)-J--chlorosulfonylphenyl 7so)-/-Pheninolator Hirazoro/
≠． 1 of Otsu was added, and then 5 ml of pyridino was added. After stirring at room temperature for 7 hours, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. 7. Recrystallize from N,N-dimethylacetamide methanol. I got it at 7pm.

m. p, II ta~/de/'C Synthesis Example 11 Synthesis of Dye-Donating Substance (2) 2-(teramino-2-(2-methquinethoxy)benozenos/L.honinoleamino ψt) obtained in Synthesis Example 7 - Dissolve 6.3 g of petit router hexadesol quinophenol in 30 yd of N,N-dimethynoleacetamide,
y:/)-t-(darchlorosulfonylphenyl)-s
-Hee-yno'oys. Add oy and then add pyridinta m
Added l.

After stirring at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. Recrystallize with acetonitrile and g
．． ≠g was obtained.

m, p. /≠j~/≠ta0C Synthesis Example/2: Synthesis of dye-donating substance (1o) 1-amino≠1-t-guthylterhexadenyloxyphenol hydrochloride tt. tiy and Hi Koichi C3-chlorosulfonyl≠1 (j-methquinetoquine)phenylazo), 2-
(N,N-Diethylsulfamoyl)-termethylsulfonylamino-/-naphthol J,f'f:N,N-
Dissolve pyridine 7'l in dimethylacetamide 20111
, 2gl were added. /time. After stirring at 2t'c,
The reaction solution was poured into dilute hydrochloric acid. The precipitated solid was collected and purified by silica gel column chromatography (eluted with a mixed solvent of chloroform-ethyl acetate (.2:/)).

Yield j, 29.

Synthesis Example/3: Synthesis of dye-donating substance (17) 1-Amino≠1-t-butyl! -hexadenyloxyphenol hydrochloride//. /l”&N,N-dimethylacetamide i
It was dissolved in oomt and 2 ml of Pirint was added. To this, Yuichi(3-chlorosnorefonylbenzenesulfonylamine)-λ1(N-L-7'-F-lsulfamoyl)-
4-(2-Methynolesulfonylu≠-2]-rofueninoleaso)-/-1-phthol 20! added. After stirring for / hour, the precipitate was poured into 500 ml of ice water and recrystallized with isoprobil anolecono[·-acetonitrile (/:/). I got gg.

Synthesis Example/4L=Synthesis of dye-donating substance (19) λ-[j
-amino-2-(21methoxy/tech1.ki/)benzenesulfonylamino]1≠-L-F'thyl-j-hexate/
Ruoki/phenonore 3/, evening, s- (J-1 rosulfonyl benozenosnorefonylamino) 1≠1 (2-methylsulfonyl ≠ 12 phenylazo) -/-f
Futonore 3ta. /f was dissolved in N,N-dimethylacetamide/00ml, and pyridi/2/ml was added. to
After stirring for 2 minutes, methanol 2. rOπt1 water/θOtnl was added. The precipitated resinous material solidified after a while, so it was collected. This is toluene-methanol water (/t
:lI-:3) Recrystallized from the mixed system to obtain a/,sg.

Synthesis Example/j Synthesis of Compound HiroO a). 2. Synthesis of terdihydroquino/1≠1 t-butylacetophenone [-butylhydroquino 7f39 was dissolved in acetic acid OOd and heated to go ~ taOOC while boron trifluoride (BF
3) was introduced for about 3 hours.

After the reaction is complete, pour the precipitated viscous solid into 1/l of ice water.
I took it. This solid. It was dissolved in 2N-NaOH&00$l and the insoluble portion was removed. 'PtL was made acidic with dilute hydrochloric acid, and the precipitated crystals were collected, washed with water, and then recrystallized from aqueous methanol.

Yield: 619 (#%) b) λ,j-dihydride 7-≠1E-butylacetate 1.pheno/, synthesis of oxome 1. Keto/. obtained in step a). 27g to 70% ethanol
Heat and dissolve with ynl% sodium acetate 2≠7,
Hydroquinylamine hydrochloride/2f/ is added to 70% of water while stirring.
ml of the solution was added and refluxed for about 1 hour. After the reaction was completed, the mixture was poured into 00@1 ice water, and the precipitated crystals were collected and recrystallized from benzene-hexane.

Yield 7.7! /(7&%) C) Synthesis of I,-t-butyl router hydroxy-7-2-methylbenzoxazone. I7 in acetic acid/00ml
Introducing dry hydrochloric acid gas while dissolving and heating the /.
．． Refluxed for 5' hours. After the reaction was completed, it was poured into SOOml of ice water, and the precipitated crystals were taken out of the furnace and washed with water.

Yield qy ("yo%) d) Otsu-L-butyl router to xade/noleoxy-2-
Synthesis of Methylbenozoxazole The benzoxazole t. obtained in C) above. 'yq dimethylformamide som
The solution was stirred at go-4o0C for 6 hours with gq of anhydrous potassium carbonate and gq of hexadecynorepromid//q.

After the reaction is complete, remove the inorganic substances and add methanol/O2 to the P solution.
ml was added and cooled on ice to precipitate crystals. The title compound was obtained by filtering this.

Collection 1 item, gyr 3.2 section) c). Synthesis of 2-amino-j-L-butyl≠-hexade/luoki/phenol hydrochloride 7.3 da of the x-doxazole compound obtained in h4e') was refluxed for 3 hours with 30 ml of ethanol and 20 ml of concentrated hydrochloric acid. After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were collected and washed with water, and then with acetonate.

Yield Z. 7g (7.2%) f) Synthesis of Compound Example 4l-0 Hydrochloride ty obtained in L e) and sulfonyl chloride I, g'9f dimethylacel amide 30n of the dye having the following structural formula
After the reaction was completed, it was poured into dilute hydrochloric acid and the precipitated crystals were collected and washed with water.

After drying, the residue was purified by silica gel chromatography to obtain 2.2 g of the title compound containing substantially all of the components.

Dye Sulfonyl Chlorite: Synthesis Example/B: Synthesis of Dye-Donating Substance (42) Above Synthesis Example/! In d), instead of ot-1-butinol-hydroquine-2-methyl
Hexadenylation of 01 was carried out using -octylterhydrogen/-comethylbe/suoxazole. Next, a dye-donating substance (42) was obtained by the same treatment as in Synthesis Example 3e) and f).

The dye-donating substance of the present invention is disclosed in U.S. Patent No. 2,322,02
It can be introduced into the photosensitive material by a known method such as the method described in No. 7. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl esters (diphthyl fucrate, dioctyl phthalate-1, etc.), phosphoric acid esters (diphenyl phosphate, 1-riphenynolene J; spha-1-2 tricresinole phosphate, dioctyl butyl phosphate-1, etc.) , citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), 1-rimesin Acid esters (e.g. tributyl l-rimesonate)
High boiling point organic solvents such as
Organic solvent at 0°C. For example, it is dissolved in a lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., and then 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 a polymer described in No. 3 can also be used. In addition, various surfactants can be used when dispersing dye-donating substances in hydrophilic colloids, and these surfactants are described elsewhere in this specification as surfactants. You can use the ones listed.

The amount of the high boiling point organic solvent used in the present invention is 10 g Ju or less, preferably 5 g or less, per 1 g of the dye-donating substance used in G1.

In the present invention, a reducing agent can be used if necessary. The reducing agent in this case is a so-called auxiliary developer.
It is oxidized by a silver halide and/or an organic silver salt oxidizing agent, and its oxidized product has the ability to oxidize the reducing substrate Ra in the dye-donating substance.

Useful auxiliary developers include alkyl-substituted hydroquinones such as hydroquinone, t-butylhytroquinone, 2,5-dimethylhydroquinone, halogen-substituted hydroquinones such as catechol, pyrogallol, chlorohydroquinone and dichlorohydroquinone, and methoxy Examples include anoleni-I-substituted hydroquinones such as hydroquinone, and polyhydroxyhensen derivatives such as methylhydroxynafculene.

Furthermore. Methyl gallate, ascorbic acid, ascorbic acid derivatives. Hydroxylamines such as N,N'-di-(2-ethoxyethyl)hydroxylamine, 1-FJ. Vilazolidones such as 3-viraduritone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, reductones, and human cyditetronic acids are useful.

Auxiliary developers can be used in a range of concentrations. A useful concentration range is 0.0005 times molar to 20 times molar relative to silver, and a particularly useful concentration range is 0.0005 times molar to 20 times molar. It is 0.001 times mole to 4 times mole.

Various dye release aids can be used in the present invention. A dye release aid is a photosensitive agent that promotes the oxidation-reduction reaction between a photosensitive silver arsenic and/or an organic silver arsenic agent and a dye-donating substance, or releases an acid in the subsequent dye release reaction. A base 1 or a base precursor is used as a substance that can act nucleophilically on a dye-donating substance to promote dye release.

In the present invention, it is particularly advantageous to use these dye release aids to accelerate the reaction.

Examples of preferred bases include amines, including trialkylamines, hydroquinyl amines, aliphatic polyamines, N-alkyl substituted aromatic amines,
Mention may be made of N-hydroxy/alkyl substituted aromatic amines and bis[p-(dialkylamino)phenyl]methanos. Also, U.S. Patent No. 2, I/. /0,1.
In the ≠ψ issue, betai/tetramethylammonium iodide, diaminobutane dihydrochlorite is
, evening 0 otsu, tAII. Organic compounds containing amino acids such as urea and aminocaproic acid are described in the ≠ number and are useful. The basic component is released by heating the base precursor. An example of a typical base structure is described in British Patent No. Preferred base precursors are salts of carboxylic acids and organic bases; useful carboxylic acids include 1-lichloroacetic acid, trifluoroacetic acid, and useful bases include guanidine, Viberi/no, morpholino, r)-}luigi/ ,! There is such a thing as bicolin. U.S. Patent No. 3. ．． The guanidine trichomeroacetic acid described in No. 220, ♂φ O is particularly useful. Unexplored Japanese Patent Publication 50-22t
The altonamide base described in Publication No. 2j decomposes at high temperature to produce a base and is suitably used.

These dye release aids can be used in a wide variety of ways. The useful range is less than jO weight/weight/g-cents, more preferably o
,oi weight・? - cents to Iio weight percent.

In the heat-developable color light-sensitive material of the present invention, it is advantageous to use a compound represented by the following general formula because development is accelerated and dye release is also promoted.

[General formula]

In the above formula, A1, A2, A3, and A4 may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a chloroalkyl group, an aralkyl group, an aryl group, a substituted aryl group, and a heterocyclic residue. Represents substituents accumulated from within, and also represents A1 and A2 or A3 and A
4 may be connected to form a ring.

Specific examples include H2NS02NH2, H2NS02N
(CH3)2,H2NS02N(C2I1.)2,1-
INSONHCH,'H2NS02N(C2H401{
)2,223CHNHSONHCH3,32 and the like.

The f-hybrid compounds mentioned above can be used in a wide range of applications.

A useful range is 20 weight cents or less, more preferably 0.9 cents by weight, based on the weight of the coated dry film of the photosensitive material. /
From/to weight percent.

In the present invention, it is advantageous to use a water-releasing compound because the dye-releasing reaction is accelerated.

A water-releasing compound is a compound that decomposes and releases water during thermal development [
It refers to hi-go-mono. These f-bicompounds are particularly known for transfer printing of textiles, and are patented in Japan! ;0-41311
, NU4Fe(S04)2/2H2 described in the publication issue
0 etc. are useful.

However, in the present invention, it is possible to use a compound that simultaneously measures development activity and image stability.

Among them, inothiuroniums typified by 2-hydroxy7ethylisothiuronium licroacetate described in U.S. Patent No. 3,30/A7g, U.S. Patent No. 3,
What kind of bisinothiuroniums is /,g-(3,1,1-dioxaoctane)bis(inothiuronium trifluoroacetate 1.) described in Otsuta, T70, West German Patent No. 2?
, /12, 7l II publication, US patent ≠, 0/2, 2AO described! -Amino! -thiasorium trichloroacetate 1., 1-amino-1
-Promo Ejil-. 2-Thiazolium trichloroacetate i Which thiazolium compounds, U.S. Patent No. tt
t,ot>o,p. Bis(.2-amino-
2-f Asorium) methylene bis(sulfonylacetate), co-amino-2-tibuzolium phenylsulfonylacetate, etc., containing α-sulfonylacetate in the acidic moiety, U.S. Patent No. 1.0 and ．． As the acidic moiety described in item 7, cocarboxylic rupoxyamides are preferably used.

In the present invention, a hot solvent can be contained.

The term "thermal solvent" as used herein refers to a non-hydrolyzable organic material that is solid at ambient temperature, but exhibits a full mixed melting point in combination with other components at temperatures below the heat treatment temperature used. Useful thermal solvents include arsenides, which can act as solvents for developing agents, and arsenides, which are known to promote the physical development of silver salts with high dielectric constant substances. Useful thermal solvents include the polyglycols described in U.S. Pat.
2oooo polyethylene glycol, derivatives such as oleate ester of polyethylene oxide, beeswax, monostearin, -SO2-, high dielectric constant r-hybrid compounds having one C group, such as acetamide, saxonimide, ethyl group Rubame-}, urea, methylsulfonamide, ethylene carbonate, U.S. Patent No. 3, l. t
7, Polar substances described in Taj No. 9, t-hydroxy/butanoic acid rato/, methylsulfinylmethane, tetrahydrothiophene =/, /-dioxide, Research Teeth Closure Magazine / Ta7t, February issue /, /0-tecan-dimer-/re, methyl anisate, described in 2z-2gk-1,
Suberic acid biphenylene and the like are preferably used.

In the case of the present invention, the dye-donating substance is colored, and further,
Although it is not so necessary to include an irradiation prevention or halation prevention substance or dye in the photosensitive dye, in order to further improve the sharpness and sharpness, it is possible to and U.S. Patent No. 3,233, Ta, 27, ibid. ,ju
It is possible to contain filter dyes and absorbent substances as described in various specifications such as No. 7,3g No. 3, Same, Tata I;, No. 177. Preferably, these dyes are thermally decolorizable, such as those disclosed in U.S. Pat.
．． 76 evening, O/9, 3rd, 7l/- evening. No. 007,
Same No. 3, l. Dyes such as those described in /j,≠3.2 are preferred.

The photosensitive material used in the present invention may contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an AH layer, and a peeling layer. It can contain layers and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain coating aids, antistatic agents, anti-static agents, improving slipperiness, emulsification dispersion, preventing adhesion, and improving photographic properties (for example, promoting development,
Various surfactants may be included for various purposes such as high contrast, sensitization, etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene/glycol, polyethylene glycol/polypro♂lene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene Glycol norbitane esters, glycol alkyl amine mata amides, polyethylene
nonionic surfactants such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carbonate salts, alkyl sulfonate,
Alkylbenze/sulfonoate, alkylnaphthalenosnorefonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylphorioquinethylene/alkylphenyl Ethers, polyoxygenate/
Aniono surfactants containing acidic groups such as carboxylic acid groups, sulfo groups, phosphor groups, sulfuric acid ester groups, and phosphoric acid ester groups, such as ethylenoalkylinoic acid esters;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetai/suicides,
Ampholytic surfactants such as amine oxinides; anolekylamine salts, aliphatic or aromatic ≠ primary ammonium salts, heterocyclic pro-ammonium salts such as pyridinium, imidanolium, and phosphonium or snorephonium containing aliphatic or heterocyclic rings. Cationosurfactants such as salts can be used.

Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those in which the repeating unit of ethylene oxide is j or more.

Nonionic surfactants that meet the above conditions are widely used in fields other than the above, and their structures, properties, and synthetic methods are well known. Representative known documents include Surf
actantScienceSeriesvolume
1. Npnionic-Surfactants (Ed.
+to tedby4arLinJ+Schick, Mar
cel-DekkerInc,/FA7), 3urfa
ceAcLiveEthyleneQxideAddu
cts (by Schoufeldt.N pergamon
The nonionic surfactants described in these documents that do not meet the above conditions are preferably used in the present invention.

These nonionic surfactants may be used alone or as a mixture of two or more.

The polyethylene glycol type nonionic surfactant is used in an amount equal to or less than the weight of the hydrophilic binder, preferably less than or equal to the weight of the hydrophilic binder.

The photosensitive composition of the present invention may contain a cationic compound having a viridinium salt. An example of a cationic compound with a viridinium group is PSA Journal.
, SecLionf33 Otsu (/9 O3), USP. 2.
44Zf, l. Ott, USP3, &7/,. 24'7
, Special public Aki≠4'-30074L, Special public Akihirohiro-ta jO3
It is described in etc.

In the photographic light-sensitive material and dye-fixing material of the present invention, an inorganic or organic hardening agent may be contained in the photographic emulsion layer and other hardening layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes, (formaldehyde 1-,
cryoxal, glucuraldehyde, etc.), N=-
Methylol compounds (simethylol urea, methylol dimethylhydanyl-yne, etc.), thioxane derivatives (2.1
-dihydroxythioxane, etc.), activated vinyl compounds (
1.3.5-1-Ryacryloyl-hexahytro-S-
triazine, 1,3-hinylsulfonyl=2-probanol, etc.), active halokene compounds (2,4-cyclo-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.),
These can be used alone or in combination.

As various additives, “l%ese.archJ)isc
losurellVoI/70, t month 797g year/7
Examples of the additives described in No. 027 include plasticizers, sharpness-improving dyes, AH dyes, sensitizing dyes, capping agents, fluorescent whitening agents, and antifading agents.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the retention layer, intermediate layer, undercoat layer, backing layer and other layers are prepared for each layer using the dipping method, air knife method, curtain coating method or the like. U.S. Patent No. 3, B and/. A light-sensitive material can be prepared by sequentially coating a support onto a support using various coating methods such as the Honopur coating method described in the specification of No. 2T and drying it.

Further, if necessary, see US Patent No. 2.7t/,79/ and British Patent No. 137,09. It is also possible to simultaneously apply more than λ layer size by the method described in No. f.

Various exposure means can be used in the present invention. The latent image is obtained by single image exposure to visible radiation. In general, the light sources used for normal Fnorr printing, such as Tanogstenola/P, mercury lamp, Iodra/P, etc., Rogge/Lamp, xenon lamp, laser light source, CRT light source, fluorescent tube, light emitting diode, etc. are used as light sources. I can dig.

The original drawing may be a line image such as a technical drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original drawing may be done by overlaying the original drawing by contact printing, reflection printing, or enlargement printing.

In addition, images taken with a video camera, etc., and image information sent from a television station are sent directly to the CCTV or FOT, and this image is formed on a heat-developable material using a contact lens or a lens, and then printed. It is also possible.

Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means and display means in various devices. It is difficult to make an LED that effectively emits evening light. In this case, to reproduce a color image, three types of LEDs are used that emit green, red, and infrared light, and the parts of the sensitive material that are exposed to these lights emit yellow, magenta, and cyan dyes, respectively. Just design it.

That is, the green-sensitive part (layer) contains a yellow dye-donating substance, the red-sensitive part (layer) contains a maze/ta dye-donating substance,
It is sufficient that the infrared-sensitive portion (layer) contains a dye-donating substance. Other combinations depending on needs are also part of town Noh.

In addition to the above-mentioned method of directly attaching or projecting the original image, so-called image processing involves reading the original image illuminated by a light source using a light-receiving element such as a phototube or CCD, storing it in the memory of a computer, etc., and processing this information as necessary. There is also a method of reproducing this image information on a CRT and using it as an image-like light source, or directly causing the three types of LEDs to emit light based on the processed information for exposure.

In the present invention, after exposure of the photosensitive material, the obtained latent image is, for example, about go0c to about. Development can be accomplished by heating the element at moderately elevated temperatures, such as from about 0.S seconds to about 300 seconds at 2jO<0>C. As long as the temperature is within the above range, either high or low temperatures can be used by increasing or shortening the heating time. Especially about //O
Temperature ranges from 0.00 to about /to0c are useful.

The heating means may be a simple hot plate, an iron, a hot roller, a heating element using carbon or titanium white, or the like.

In the present invention, a specific method for forming a color image by heat development is to move a hydrophilic mobile dye. For this purpose, the light-sensitive material of the present invention has a light-sensitive layer (T) on a support, which contains at least silver halide, optionally an organic silver hydrochloride, a dye-donating substance which is also a reducing agent thereof, and a binder. and a dye fixing layer (I) that can receive the hydrophilic and diffusible dye formed by the layer (I).
II).

The above-mentioned photosensitive layer (t) and dye fixing layer (I[) may be formed on the same support, or may be formed on separate supports. Dye fixing layer (II) and photosensitive layer C
I) can also be peeled off. For example, after imagewise exposure, uniform heat development can be carried out, and then the dye fixing layer (n) or the photosensitive layer can be peeled off. In addition, when a photosensitive material in which the photosensitive layer (I) is coated on the support 7 and a fixing material in which the fixing layer (II) is coated on the support 12 are formed separately, the photosensitive material has an image-like structure. After exposure and uniform heating, the fixed dye can be overlaid to transfer the mobile dye to the fixed layer i).

There is also a method in which only the photosensitive material (1) is imagewise exposed, and then the dye fixing layer (n) is superimposed and uniformly heated.

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

The polymer mordants used in the present invention include polymers containing secondary and tertiary amine groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing quaternary cations/groups thereof, and having molecular weights of s, ooo to 20 o, ooo, especially io, oo
o-soIoooty).

For example, U.S. Pat. No. 2,617-1. jl. Hirogo, same λ, 4
Vinylpyridi/polymer and vinylpyridinium thione polymer disclosed in J4.1/-30, No. 43, /III, Otl, No. 3,7, Trill, etc.; U.S. Patent No. 3, Otsu 2. f, tta ψ, same 3l
Zajta, No. 076, Yoshihiro, /2f,! No. 3g, British Patent/,. 277, Hiroj No. 3 Specification, etc.K Polymer mordants capable of crosslinking with gelatin, etc.; U.S. Pat. No. 3, Ta'
゛r, Tade 3, same λ, 7.2/, ♂ Yu λ, 4 λ, 7
7 and 063, JP-A-5≠-//322r, same evening≠
Ichihiro j22, same! ;4! -i-! A027 Mei a
Aqueous sol type mordant disclosed in Book et al.; US Pat. No. 3,
Water-insoluble mordant disclosed in the specification of No. 17♂, OTR; U.S. Pat.
No. 7333) A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc.; furthermore, U.S. Pat. l/
-12, 3, ψgg, 706, 3,337,0
7, No. Otsu, No. 3,277, / No. 7, No. 3, . 27/,
/lI. g, JP-A-30-7/332, JP-A No. 33-3
No. 032g, same evening 2-/evening ss. zg, same evening 3-12
The mordant disclosed in the specification of No. 3 and No. 3, jj-/02≠ can be mentioned.

Other US patents λ. t73,. 3/l issue, same λ, gza2
, /Kl, may also be mentioned.

Among these mordants, for example, those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used.

Particularly preferred polymeric mordants are shown below.

(1) Groups that have an ≠-grade ammonium group and can be covalently bonded to gelatin (e.g., aldehyde group, chloroalkanoyl group, chloroalkyl group, vinylsulfonyl group, pyridinium carbonyl group, vinylcarbonyl group, alkylsulfonyl group) For example, (2) a copolymer consisting of repeating positions of a monomer represented by the following general formula and repeating units of other ethylenically unsaturated monomers, and a crosslinking agent (such as hahis-gamma lucan sulfone-+-, bis-alenosulfonate, etc.). product of the reaction with

T{. bI:H, alkyl group R52:H, argyl group, aryl group Q:. At least λ of divalent groups R53, 1 (b, 1, etc.): anolequinole group, aryl group, or bb R3 to ■t5 may be bonded to form a heterocycle.

X: aniono (the above alkyl groups and aryl groups include substituted ones) (3) Polymer X represented by the following general formula: about 0.2j
-about 0 molar coefficient y: about 0 - about 0 molar coefficient 1: about /O - about 7 molar coefficient A: monomer having at least two ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated heptadnomer Q: N, P bbb R1, R2, 几. : An alkyl group, a cyclic hydrocarbon group, or at least two of R1 to R\ may be combined to form a ring. (These groups and rings may be substituted.) (4) Copolymer-X consisting of (a), (b) and (C)
: Hydrogen atom, alkyl group or . R0, R2, R3: each represents an alkyl group, and the total number of carbon atoms in R.1 to R3 is 7.2 or more.

(The alkyl group may be substituted.) X: As the gelatino used in the aniono mordant layer, various known gelatins can be used. For example, different gelatin manufacturing methods such as lime-treated serrati/, acid-treated gelatin/, or
It is also possible to use gelatino obtained by chemically modifying the obtained seratin such as phthalation or sulfonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment.

A person skilled in the art can easily determine the mixing ratio of the polymer mordant and gelatin of the present invention and the coating amount of the polymer mordant, depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process to be used. Although a certain child is born,
Mordant/gelati/ratio is 20/10-40/. 20(-@
It is preferable to use the mordant at a coating amount of 0.s-1ff/m.

The dye fixing layer (II) may have a white reflective layer. For example, gelatin/
A layer of titanium dioxide dispersed in The titanium dioxide/layer forms a white opaque layer and a reflective color image is obtained by viewing the transferred color image through the transparent support IRII.

A typical fixative material used in the present invention is obtained by mixing a polymer containing an ammonium salt with gelatin and coating it on a transparent support.

A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer.

In a method in which the transfer aid is externally supplied, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used as the dye transfer aid. Also, methanol, N. N-dimethylformamide, acerol,
A low boiling point solvent such as diisobutyl ketone or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used. The dye transfer aid may be used by moistening the image-receiving area with the transfer aid.If the transfer aid is built into the light-sensitive material or dye fixing material, there is no need to supply the transfer aid from the outside. The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or may be incorporated as a precursor that releases the solvent at high temperatures. More preferably '%? Ju is a method in which a hydrophilic heat melting agent, which is solid and dissolves at high temperatures, is built into the photosensitive paulownia material or dye fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Also, the built-in layer may be an emulsion layer, an intermediate layer, a protective layer or a dye fixing layer. Examples of hydrophilic thermal solvents preferably incorporated into the dye fixing layer and/or its adjacent layer include 5
Ureas, bilicins, Ami F, sulfonami IS cheeks,
Imi 1 cheek, alcohol. There are oximes and other heterocycles.

Further, in the present invention, a method of heating in the presence of a hydrophilic thermal solvent may be used to transfer the dye from the photosensitive layer to the dye fixed layer. In that case, the movement of the mobile dye may be initiated simultaneously with the release of the dye or after the release of the dye has been completed. Therefore, the transfer reservoir may be heated after the heat development or at the same time as the heat development. Simultaneously with thermal development means that the heating for development also acts as the heating for the transfer of the released dye at the same time. Since the optimal temperature for development, the optimal temperature for dye migration, and the heating time required for each do not necessarily match, the temperatures can be set independently.

It is preferable to heat the dye transfer reservoir at tO'C-2!00C from the viewpoint of storage stability and workability of the photosensitive material. Therefore, a material that can act as a hydrophilic thermal solvent in this temperature range is used. It can be selected as appropriate. It is obvious that a hydrophilic thermal solvent must be able to quickly assist the movement of dyes by heating, but if we also consider the heat resistance of the photosensitive material, the requirements for a hydrophilic thermal solvent are The melting point is ≠
o'c~-2!゛0°C1 Preferably ≠o0c-koθθ
OC1 is more preferably tio0c~/jθ0C.

The "hydrophilic thermal solvent" in the present invention is a compound that is in a solid state at room temperature but becomes a liquid state when heated,
(Inorganic/Organic) value>l1 and water solubility at room temperature is defined as a compound having / or more. Here, inorganic and organic are concepts for predicting the properties of compounds, and their details can be found in, for example, the field of chemistry//7/? page(/tat
7).

Since the hydrophilic thermal solvent has the role of assisting the movement of the hydrophilic dye, it is considered that it is preferably a compound that can act as a solvent for the hydrophilic dye.

In general, a suitable solvent for dissolving an organic compound is one whose (inorganic/organic) value is the same as that of the organic compound.
It is empirically known that the value is close to the inorganic/organic) value. On the other hand, the (inorganic/organic) value of the dye-donating substances used in the present invention is approximately 1, and the (inorganic/organic) value of the hydrophilic dye that is released from these dye-donating substances is approximately 1.
The value has a value greater than the (inorganic/organic) value of the dye-donating substance, preferably /. It has a value of 1 or more, particularly preferably 7 or more. The hydrophilic thermal solvent used in the present invention is preferably one that moves only the hydrophilic dye and does not move the dye-providing substance, so its (inorganic/organic) value is /organic) value. That is, as a hydrophilic thermal solvent, it is an essential condition that the (inorganic/organic) value is / or more, preferably 1 or more.

On the other hand, from the viewpoint of molecular size, it is considered preferable that molecules that can move by themselves without inhibiting the movement exist around the moving dye. Therefore, the molecular weight of the hydrophilic heat solvent is preferably small, about 200 or less, and more preferably about 1/00 or less.

The hydrophilic thermal solvent of the present invention only needs to be able to substantially assist the movement of the hydrophilic dye generated by heat development into a fixed layer of the dye, so it can be included in the dye fixing layer. In addition, it can be contained in a photosensitive material such as a photosensitive layer, in both a dye fixing layer and a photosensitive layer, or in a photosensitive material or in an independent dye fixing material having a dye fixing layer. A separate layer containing a hydrophilic thermal solvent can also be provided. From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, it is preferable that the hydrophilic thermal solvent is contained in the dye fixing layer and/or the layer adjacent thereto.

The hydrophilic thermal solvent is usually dissolved in water and dispersed in the binder, but it can also be used dissolved in alcohols, such as methanol, ethanol, etc.

Examples of the hydrophilic heat solvent used in the present invention include ureas,
Pyridines, amides, sulfonamides, imides,
Mention may be made of alcohols, oximes, and other complexes.

The present invention will be explained in more detail with reference to Examples below.

Example 1 7110Q gelatin and 6 g of KBrx are dissolved in 1 volume of water. The solution is kept at 0°C and stirred.

IO
Add to the above solution for 1 minute.

Then, λ
Add in minutes.

The pH of the silver iodobromide emulsion thus prepared is adjusted, and excess salt is removed by sedimentation.

Then the pH was adjusted to t. A silver iodobromide emulsion with yield ip+θoy was obtained.

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

5g of yellow dye-donating substance (68), surfactant. ! : L, te, cono-citric acid monocoethyl-hexyl ester sulfonic acid nod. In the evening, we weighed 1 jg of trichlorethylene phosphate (TCP) and added 30.0 g of ethyl acetate. l
Add and heat to dissolve at about 00C to make a homogeneous solution. This solution and 70% solution of lime-treated gelatin/00fl
After stirring and mixing, io
, oooBpM. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except that the magenta/ta dye-providing substance (42) was used. Similarly, cyan dye-donating substance (69)
A cyan dispersion was made containing .

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

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

Poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is i'.i) ioy. It was dissolved in 200 Mt of water and mixed homogeneously with the lime treated gelatin, iooy. This mixed solution was uniformly applied to a wet film thickness of 0 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material having a mordant layer.

The multilayered color photosensitive material was exposed to light at 2000 lux for 0 seconds using a tungsten light bulb through a three-color separation filter of B, G, and B whose densities were continuously changed. Then on a heat block heated to /3o0C
Heated uniformly for 0 seconds.

Next, water was supplied at a rate of 30.1/m 2 to the film side of the dye fixing material, and then the heat-treated photosensitive coatings were superimposed on the fixing material so that the film surfaces were in contact with each other. ro0c
After heating for 2 seconds on a heat block, the dye fixing material was peeled off from the light-sensitive material, and yellow, magenta, and cyan color images corresponding to the BXGXR three-color separation filter were printed on the fixing material. . The maximum density and minimum density of each color are as shown in -F below.

Example 2 The method for making benzoto IJ azole silver emulsion will be described.

Ze5tin 21g and penzotriazole/3. ．． Dissolve 2f in 3000 liters of water. What about this solution? . Keep at temperature C and stir. A solution of silver nitrate/7f dissolved in water/ooytl is added to this solution over a period of λ minutes.

The pH of this penzotriazole silver emulsion is adjusted, precipitated and excess salt removed. Then p}{t. A penzotriazole silver emulsion with a yield of ≠009 was obtained.

A multilayer film as shown in the following table was prepared in exactly the same manner as in Example, except that the silver iodobromide emulsions in the actual layer, green-sensitive layer, and red-sensitive layer in Example and the above penzotriazole silver emulsion were used in combination. I made a color photosensitive material with the following composition.

The same operation as in Example 1 was carried out, and the following yellow, magenta, and cyan color images were obtained corresponding to the BXG and R filters.

Example 3 A color light-sensitive material having a multilayer structure as shown in the following table was prepared in exactly the same manner as in Example λ except that the sensitive spectral region of the emulsion was different.

A tungsten light bulb is used in the multi-layered color photosensitive material described above, and a G1 and industrial three-color separation filter (G is 3oo-to (7nm% is 7.0
0-700nm pando/κ filter, IRl”l
After exposure at λ,000 lux for 10 seconds through a filter that transmits at least 700 nm, the operation was carried out in exactly the same manner as in Example.

A three-color image as shown below was obtained on the dye-fixing material.

Example 4 A method of producing a dye fixing material different from Example 4 will be described.

Poly(methyl acrylate-co-N,N.N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is /:/)/09 was dissolved in 200@l water, /
o% lime-treated gelatin toog. Pour this mixture onto a polyethylene terephthalate film.
It was applied uniformly to a wet film thickness of μm.

On top of this, the following (a) to (e) were further mixed and dissolved, and then a dye transfer aid layer was uniformly applied to a wet film thickness of 10 μm and dried.

(a) Urea gf (b) 1 yptl of water (C) /O weight aqueous solution of polyhinyl alcohol (degree of saponification) /2// (d) j% aqueous solution of the following compound 2 yttt (e) Dodecyl Tati aqueous solution of sodium benzenesulfonate O. Yumura: The multilayer photosensitive material prepared in Example 1 was heated under an exposure source in the same manner as in Example 1.

Next, this and the dye fixing material of this example were shielded together so that the film surfaces were in close contact with each other (immediately after passing through a pressurized/30'C heat roller)/onto a tort block heated to 20°C. The mixture was heated uniformly for 30 seconds. Thereafter, when the dye-fixing material was peeled off from the light-sensitive material, yellow, maze/ta, and cyan color images as shown in the following table were obtained on the dye-fixing material.

[Brief explanation of drawings]

Figures 1 to 1 show the layer structure of the photosensitive material used in the present invention. In the figure, BLXGL, }I, L, and IRL indicate blue-sensitive, green-sensitive, and red-sensitive emulsion layers, respectively, and (C.), CM), and (Y) shown below indicate cyan, cyan, and red-sensitive emulsion layers, respectively.
Indicates that magenta and yellow dye-providing substances are included. Further, YF represents a yellow filter layer, ◯L represents an intermediate layer, PC represents a protective layer, and S represents a support. Furthermore, CLXML,
'YL represents a non-photosensitive hydrophilic colloid layer containing cyan, magenta, and yellow dye-providing substances, respectively.

Claims (1)

[Claims] The support has at least three silver halide emulsion layers sensitive to different spectral regions7, and each emulsion layer and/or a non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer has a photosensitive layer. A multilayer containing a dye-donating substance that is reducible to photosensitive silver halide and that reacts with photosensitive silver halide upon heating to release yellow, magenta, and cyan hydrophilic dyes/species. A method of heating a light-sensitive material in a substantially water-free state at the same time as or after image exposure to form a movable dye all over image.