JPS59174832A - Dry type image forming method - Google Patents

Abstract

PURPOSE:To obtain a dry type image superior in tone, etc. by imagewise exposing a positive type silver halide photosensitive material of a specified constitution, heat developing it, transferring a mobile dye formed in the unexposed areas with a hydrophilic hot solvent, and fixing it to a fixing layer. CONSTITUTION:A positive type silver halide photosensitive material is prepared by forming on a support a layer contg. photosensitive silver halide, a binder, an electron donor, e.g. formula I , and/or an electron transfer agent, e.g. hydroquinone, a reducible dye releasing agent, e.g. formula II, and a hydrophilic hot solvent, e.g. N-methylurea and pyridine-N-oxide. This material is imagewise exposed, and after that or at the same time as that, it is heat developed, a mobile dye formed in the unexposed areas is transferred in the presence of the hydrophilic hot solvent in a high temp. state, and it is fixed in a dye fixing layer to form a dry method image.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a completely dry image forming method. More specifically, the present invention relates to a method of fixing a dye obtained in an unexposed area by heat development treatment to a dye fixing layer by heating without using a system containing a solvent.

Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and contrast adjustment compared to other photographic methods such as electrophotography and diazo photography. Ta. In recent years, a technology has been developed that allows images to be formed easily and quickly on photosensitive materials using silver halide by changing from the conventional wet processing using a developing solution to a dry processing using heating, etc. It's here.

Heat-developable photosensitive materials are well known in the art, and for information on heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" (published by Corona Publishing, 1979), pages 553-55.
5 pages, video information published in April 1978, 40 pages, Neble
tts Hand-book of Photo
graphy and reprography 7
thEd.

(Van Nostrand ReinholdC
US Pat. No. 3,152.904, No. 3,301,6.
No. 78, No. 3,392,020, No. 3.457,07
No. 5, British Patent No. 1,131゜108, No. 1,167
．． No. 777 and Research Disclosure Magazine 19
It is described in the June 1978 issue, pages 9 to 15 (RD-17029).

Regarding the method of obtaining a color image by a dry process, many methods have already been proposed. Regarding a method of forming a color image by combining an oxidized product of a developer and a coupler, U.S. Pat.
No. 531,286, p-phenylene diamine reducing agents and phenolic or active methylene couplers; US Pat. No. 3,761.270, p-aminophenolic reducing agents; Belgian patent No. 802. 19th issue and 2nd issue - Disclosure magazine September 1975 issue 31~
On page 32, a sulfonamidophenol reducing agent is proposed, and in US Pat. No. 4,021,240, a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler is proposed.

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

In addition, a nitrogen-containing heterocyclic group is introduced into the dye to form a silver salt,
A method of releasing dyes by heat development is described in Research Disclosure magazine, May 1978 issue, pages 54-58 (R
D-16966). This method is not a common method because it is difficult to suppress the release of dye in areas not exposed to light, making it impossible to obtain clear images.

Further, regarding the method of forming a positive color image by thermal silver dye bleaching method, see, for example, Research Disclosure Magazine, April 1976 issue, pages 3o to 32 (RD-14433).
, December 1976 issue of the same magazine, pages 14-15 (RD-152
27) and U.S. Pat. No. 4,235,957, useful dyes and bleaching methods are described.

However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the cleanliness of the dye, and the resulting color image is gradually reduced by coexisting free silver, etc. Since it is bleached, it has the disadvantage of not being able to withstand long-term storage.

Also, regarding the method of forming color images using leuco dyes, C.
For example, U.S. Pat. No. 3,985,565, U.S. Pat.
No. 022,617. However, this method has the disadvantage that it is difficult to stably incorporate Roini I dye into the photographic material, and the material gradually becomes colored during storage.

The present inventors have already provided a new photosensitive material capable of overcoming the drawbacks of these conventional methods, and have also provided an image-forming method (Japanese Patent Application No. 56-157, 798).

This is a photosensitive material that can release a mobile hydrophilic dye by a simple method of heating in a substantially water-free state, and this mobile dye is fixed mainly in the presence of a solvent. The invention relates to an image forming method characterized by moving the image to -.

As a result of further research into the above invention, the present inventors have discovered that a mobile hydrophilic dye formed by heating in a state substantially free of water can be produced by supplying no solvent at all. It has been discovered that it can be easily moved by heating it further, and the present invention has been achieved.

Therefore, the first object of the present invention is to develop a hydrophilic dye produced by heat development treatment performed after or simultaneously with exposure.
In particular, it is an object of the present invention to provide a method for fixing a dye to a dye fixing layer without supplying a solvent from the outside.

A second object of the present invention is to provide a method for fixing a plurality of hydrophilic dyes produced by heat development treatment performed after exposure or simultaneously with exposure to a dye fixing layer without particularly supplying a solvent from the outside. It's about doing.

That is, the present invention provides a positive silver halide photosensitive material containing at least a photosensitive silver halide, a binder, an electron donor and/or an electron transfer agent, and a reducible dye releasing agent on a support after imagewise exposure or The hydrophilic dye generated in the unexposed area by heat development treatment at the same time as image exposure is transferred to the dye fixing layer under high temperature conditions in the presence of a hydrophilic hot solvent, without particularly supplying a solvent from the outside. , is a dry image forming method characterized by forming a positive dye image.

In the light-sensitive material according to the present invention, heating in a substantially water-free state after imagewise exposure or simultaneously with imagewise exposure causes undeveloped silver halide to be formed in the unexposed areas in addition to the silver image. Correspondingly, hydrophilic mobile dyes are obtained. In the present invention, this heat development process is referred to as "heat development process", but in this case, since the dye obtained in the unexposed area is a hydrophilic mobile dye, the hydrophilic dye has an affinity for The dye can be transferred to the dye fixing layer in an atmosphere having a high temperature, thereby obtaining a dye image with excellent image quality and storage stability.

This step is the "dye fixation" step in the present invention.

In this case, it has already been disclosed that an atmosphere having affinity with the hydrophilic dye can be realized mainly by supplying a solvent (Japanese Patent Application No. 56-157, 7
98), Furthermore, in the present invention, by making a hydrophilic thermal solvent exist, an atmosphere having affinity with the hydrophilic dye is realized, so there is no need to supply a particular solvent, and therefore, from exposure to heat development and In all steps up to dye fixation, a completely dry process that does not require any external solvent supply makes it possible to form a dye image with good color and image reproducibility.

This principle remains essentially the same whether an autopositive emulsion or a negative type emulsion is used as an emulsion for a light-sensitive material. A dye image with good color and image reproducibility can be obtained in the same manner as when using a negative emulsion, except that only the dye image among the silver image and mobile dye image is transferred to the dye fixing layer. .

The heat development treatment in the present invention is substantially carried out by heating water at a temperature of 1 hour; heating here means heating at 80°C to 250°C; A state in which the reaction system is essentially water-free means that the reaction system is in equilibrium with moisture in the air, and water is not specifically supplied to trigger or accelerate the reaction. The situation is “T k> e t h e o
ry o f t h ephotograp
hic process”4ill Ed, (
Edited by T. H. Jarnes, Ma.
crnillan) 374i.

, 4-In the invention, the dye to be released can be selected by selecting various compounds as the reducible dye-releasing agent, so that various colors can be reproduced.

Therefore, by selecting a combination, it is possible to create a colored image, so the dye image in the present invention includes not only a monochrome image but also a multicolor image, and a monochrome image also includes a monochrome image obtained by mixing two or more colors. .

In the method for forming a dye image of the present invention, a diffusion-resistant dye-donating substance (herein referred to as a reducible dye) that does not originally release a hydrophilic dye but releases a hydrophilic dye upon reduction. By using a releasing agent (referred to as a releasing agent), by imagewise exposure and heat development, the exposed photosensitive silver halide is used as a catalyst to combine the photosensitive silver halide with a reducible electron transfer agent and/or electron donor. A redox reaction occurs between them, a silver image is generated in the exposed area, and the electron transfer agent and/or electron donor is oxidized. On the other hand, in the unexposed area, the reducible dye-releasing agent reacts with the remaining electron transfer agent and/or electron donor as an inverse function of the silver image, and as a result is reduced to a reduced form, and therefore , a hydrophilic mobile dye is released into the unexposed area.

A first example of a compound referred to as a reducible dye-releasing agent for use in the present invention includes pallast-stabilized compounds that undergo intramolecular nucleophilic substitution to release a mobile dye.

The ballast stabilizing compound contains a precursor of a nucleophilic group that must accept at least one electron before the compound can undergo intramolecular nucleophilic substitution.

The reducible dye releasing agent used in the present invention is an electron donor (
That is, compounds that are useful in combination with compounds that are reducing agents and provide the necessary electrons to enable the reducible dye-releasing agent to be reduced to a form that undergoes intramolecular nucleophilic substitution. It is. When the electron donor is rendered imagewise dispersed in the photographic element upon exposure to light,
Electrons are donated from the electron donor to the ballast-stabilized electron-accepting nucleophilic substitution compound in an imagewise pattern, resulting in subsequent imagewise displacement and dye release.

A first reducible dye releasing agent of the present invention found to be particularly useful in heat-developable color photographic processes and photographic elements.
The compound can be represented by the following model formula.

(ballast-stabilized carrier) is 1
Ballast-stabilized carriers include compounds having one or more mobile moieties attached to one ballast group or compounds having one or more ballasts attached to one movable moiety; a group capable of rendering the compound immobile under diffusion transfer conditions; the ballast-stabilized carrier, upon accepting at least one electron, It contains a group that provides a cleavage group and a group that can undergo intramolecular nucleophilic substitution.

The reducible dye-releasing agent contains an electrophilic leaving group in each linking group linking the ballast-stabilized carrier to its respective mobile component, and the nucleophilic group generated by reduction is As a result of reacting with the electrophilic leaving group, some groups remain with the ballast stabilized carrier and some groups remain with the mobile moiety.

In general, an intramolecular nucleophilic substitution compound has a nucleophilic group and an electrophilic group that coexist in close proximity in the three-dimensional structure of the molecule and can therefore cause an intramolecular substitution reaction. In the present invention, intramolecular nucleophilic substitution occurs after a nucleophilic precursor accepts at least one electron. In this case, the electrophilic and nucleophilic groups may be any compound in which these groups are held in a reactive position (polymeric compounds, macrocyclic compounds, polycyclic compounds, enzyme-like structures, etc.). )
It can be used inside. However, the nucleophilic group and the electrophilic group preferably occupy any position in the organic ring or in the organic compound that easily forms an organic ring by intramolecular reaction. The electrophilic group is at a position capable of forming a 3- or 5- to 7-membered ring, more preferably a 5- or 6-membered ring (4-membered rings are generally difficult to form in organic reactions). It has been known).

In this way, the intramolecular nucleophilic substitution compound according to the present invention is
Although relatively reactive, they must be stable under the processing conditions unless the initial release of the hydrophilic dye compound occurs as a direct function of the reduction of the nucleophilic precursor group. be.

The reducible dye-releasing agent used in the present invention comprises a nucleophilic precursor group and an electrophilic cleavage group (c
levage group). This bonding group may be an acyclic group, but is preferably a cyclic group. In one highly preferred embodiment,
Both the nucleophilic precursor group and the electrophilic group are bonded to the same aromatic ring structure, and the ring structure in this case may be a carbocyclic structure or a heterocyclic structure, Additionally, fused rings are included, such that each group can be present on a separate ring. In particular, it is preferred that both groups are directly bonded to the same aromatic ring, and in this case, it is particularly preferred that the aromatic ring has a carbocyclic structure.

A first preferred embodiment of the reducible dye-releasing agent of the present invention has 1 to about 5 atoms, preferably 3
or 4 atoms, and can be represented by the following general formula.

General formula (1) In the formula, W, x, y, z, n and m are positive integers 1 or 2, and ENtlP is an electron-accepting nucleophilic group precursor, for example,
Precursor of hydroxyamino group [nitroso group (No),
[containing a stable nitroxyl free radical (N-0. is hydrolyzed to an oxo group before accepting an electron in an alkaline environment), and R1 is an organic group containing up to 50 atoms, preferably up to 15 atoms, preferably a cyclic organic group. (including a cyclic group having a bridge), or a polycyclic group (preferably having 5 to 7 atoms in the ring to which ENuP and E are bonded), more preferably 5 to 7 atoms in the ring. Aromatic ring having 6 members or a carbocyclic ring, such as a benzonoid group, or a heterocyclic ring containing a non-aromatic ring (ENuP is part of the ring, i.e. ENuP has a nitrogen atom in the ring) is a nitroxyl group). R2 and R3 are 21iIli organic groups containing 1 to 3 atoms in the divalent bonding group, which may be alkylene groups, oxaalkylene, thiaalkylene, azaalkylene, alkyl- or aryl-substituted It may also be nitrogen. This is a group containing at least 8 carbon atoms that contains a large group in the side chain on the linking group and can function as a ballast; these groups are It is xl. As a specific example of this, for example, R3
is a dialkyl-substituted methylene bond, e.g., Q is an oxygen atom and R1 and E N u P are dimethylalkylene, which is useful when forming a guinone; E and Q provide an electrophilic cleavable group. , where E is the center of electrophilic reaction, preferably thiocarbonyl (-CS-
) group or a sulfonyl group. ;
Q is a group that provides a monoatomic bond between E and X2,
Here, a monoatom is a nonmetallic atom of group Va or VIa of the periodic table in a valence state of -2 or -3, such as an oxygen atom, a sulfur atom, and a selenium atom, preferably a nitrogen atom providing an amino group. It is an atom. These atoms provide two covalent bonds linking X2 together, so that
When forming a 5- to 7-membered ring with these atoms, and when these atoms are trivalent atoms, hydrogen atoms, 1 to 20
alkyl groups (including substituted carbon atoms and carbocyclic groups) containing preferably 1 to 10 carbon atoms, or aryl groups (also substituted aryl groups) containing 6 to 20 carbon atoms. ) can be mono-substituted.

Such examples include, for example, pyridine or piperidine groups.

, XI is a substituent on at least one of R1, R2 or R3, and one of X1 or Q-X2 is
One represents a ballast group of sufficient size to render the compound immobile in the layers of the photographic element, the other being a photographically useful dye or precursor thereof. Xi and Q-X2 also include the bonding groups necessary to link the respective moieties to E or R1. : R1, R2 and R3 are chosen to provide substantial proximity of ENuP to E to allow intramolecular nucleophilic release of Q from E. These are chosen to provide 1 or 3 to 5 atoms between the atom serving as the reaction center for the nucleophilic reaction and the atom serving as the reaction center for the electrophilic reaction, thereby may form a 3- or 5- to 7-membered ring, preferably a 5- or 6-membered ring, upon intramolecular nucleophilic substitution of the group Q-X2 from said electrophilic group. do. For example, E
is a carbonyl group, and Q is an amino group, preferably an alkyl- or alkyl-substituted amino group, X2 is bonded to Q via a sulfonyl group, and the release of Q-X2 causes the sulfonyl group to become provided.

In the compound of general formula (1) above, the stability and release rate of the electrophilic cleavable group can be controlled by using a certain atom or group in the bonding group adjacent to the -(E-Q)- group. It can be changed by When E is a carbonyl group and ENuP is an oxo group, in other certain cases, it is desirable to have an amino group in R3 immediately next to E. In some embodiments, it is also desirable to have a specific group immediately adjacent to Q in the linking group, in which case (Q-X2) becomes the group (Q-R9-X3).

Here, R9 is a group such as an aromatic group as defined hereinafter.

The properties of the ballast group in the compound of general formula (1) above are:
There is no particular restriction as long as the portion of the compound on the ballast side of E primarily provides an immobile function. E
The other portion of the molecule on the remaining side generally contains sufficient solubilizing groups to make it mobile after release and mobile in alkaline media. Therefore, if R1,
Xl may be a relatively small group provided that the remainder of R2 and R3 provides sufficient insolubility to the compound to render it immobile. However, Xl or (Q
If -X2) performs the function of a ballast, they generally consist of long-chain alkyl groups and aromatic groups of the benzene and naphthalene series. Typical useful ballast functional groups contain at least 8 or more carbon atoms, preferably at least 14 carbon atoms. If Xl is a ballast, it can be one or more groups substituted with R1, R2 or R3 that provide the desired immobility. Thus, for example, two small groups, for example two groups containing 5 to 12 carbon atoms, can be used to obtain the same immobility as one long ballast group containing 8 to 20 carbon atoms. When a large number of ballast groups are used, it may be convenient to bond the main portion of the ballast group to the aromatic ring to which it is bonded via an electron-withdrawing group.

As used herein, the term "nucleophilic group" refers to an atom or group of atoms having a pair of electrons capable of forming a covalent bond. Groups of this type are often ionizable groups that react as anionic groups. The term "electron-accepting nucleophilic precursor group" refers to a precursor group that accepts at least one electron to provide a nucleophilic group after being reduced. The electron-accepting nucleophilic precursor group has a structure that is less nucleophilic than a reduced group or has a structure that makes it difficult to approach the reaction center of a nucleophilic reaction.

A nucleophilic group is a nucleophilic group such as an oxygen atom in a hydroxyl group.
It may also include one or more. A nucleophilic group may contain one or more atoms that can serve as a reaction center for a nucleophilic reaction, such as in the case of hydroxylamino, where either a nitrogen atom or an oxygen atom can serve as a reaction center for a nucleophilic reaction. can. When there is one or more atoms that can serve as reaction centers in the nucleophilic group on the intramolecularly nucleophilically substituted compounds of the present invention, nucleophilic attack and substitution can generally result in the formation of the most favorable ring structure. This occurs as reaction intermediates pass through. That is, if the oxygen atom of the hydroxylamino group often forms a 7-membered ring and the nitrogen atom often forms a 6-membered ring, the most active reaction center for the nucleophilic reaction is , generally can be said to be a nitrogen atom.

As used herein, the term "electrophilic group" refers to an atom or group of atoms that can accept a pair of electrons to form a covalent bond. Typical electrophilic groups are sulfonyl (-502-), carbonyl (-Co-), and thikiocarbonyl (-CS->), in which the carbon atom of the carbonyl group or the sulfur atom of the sulfonyl group is It serves as a reaction center for electrophilic reactions of the group and can be partially positively charged.

Next, the term "'electrophilic cleavable group" herein refers to
Used to refer to the group (-E-Q-).

Here, E represents an electrophilic group, and Q represents a leaving group that provides a monoatomic bond between E and X2.
oup), where the monoatom is a nonmetallic atom with a valence of 2 or 3. The leaving group is capable of accepting a pair of electrons released from the electrophilic group. When the nonmetallic atom is a trivalent atom, for example, a hydrogen atom, an alkyl group (including substituted alkyl groups and a cycloalkyl group), an aryl group (including a substituent aryl group), or a 5 such as pyridine or piperazine groups
It can be substituted with a substituent selected from the atomic groups necessary to form a ~7-membered ring. In some embodiments, the methylene group, i.e., -CH2-, is represented by the above general formula (I), where m is 2.
It can be used as an electrophilic group when In this case R3 is an alkylene group containing a disubstituted methylene group, such as a diethylmethylene group or a diarylmethylene group, which is directly bonded to the aromatic group provided by R1. In this embodiment, X2 can include a carbonyl, sulfonyl, or phosphono group attached to a leaving group, such that the reaction can release a carboxy, sulfonate, or phosphonate group. 2 in the bond between the nuclear group and the electrophilic cleavable group
The presence of a substituted methylene group apparently makes the released group orient more favorably, thereby increasing the reaction rate of intramolecular nucleophilic substitution when the methylene group is used as an electrophilic group.

The reducible dye-releasing agents of the present invention can contain substituents that change the reaction rate of the compound. Such substituents are located, for example, on the cyclic aromatic group represented by R1, but especially when ENuP is a nitro group, E
The number of aromatic rings to which N u, P and Xl are bonded is small (one, preferably two electron-withdrawing groups)
on withdrawing group). These electron-withdrawing groups are positive 1-1am1-
Those having a sigma value of 1a, such as sulfonyl groups.

In cases where the electron-withdrawing substituent is located on the RI,
The reducible dye-releasing agents of the present invention represented by general formula (I) can generally be used with a wider variety of electron donors in order to more easily undergo reduction. However, for other reducible dye-releasing agents according to the present invention, it is necessary to use more powerful electron donors to achieve fast reduction rates. For example, in one embodiment where the nucleophilic precursor group is a nitro group, in order to achieve the desired reduction rate with the preferred benzisoxacilone electron donor, at least two electron-withdrawing groups must be present on the aromatic ring. used above.

As used herein, the term "immobile" is used in the sense commonly used in photography.

The word "immovable" is also used in the same sense.

The term “mobile” when used in reference to the materials of the present invention refers to
It means the opposite of the above. .

In certain embodiments, useful reducible dye-releasing compounds of the invention are ballast-stabilized compounds having the structure:

where ENuP is an electron-accepting nucleophilic precursor for a hydroxy nucleophilic group (containing an imino group and preferably an oxo group) and iQI is an imino (including alkylimino) group, a sulvony, a mido group, cyclic group formed with R4 or R6 or any group selected from the groups specified for ENuP, preferably in which G1 is in a separate position relative to ENuP above; E is The electronic group may be either a carbonyl-co- or a thiocarbonyl-C8- group, preferably carbonyl; Q is a group providing a monoatomic bond between E and R9; Here, a single atom is a nonmetallic atom in a -2 or -3 valence state of group Va or group Vla of the periodic table, such as a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom. . In this case, said atoms provide two covalent bonds linking E to R9, and if Q is a trivalent atom, e.g. a hydrogen atom, an alkyl group (1 to I(1)
containing a substituent alkyl group),
Aromatic group (containing 5 to 2 carbon atoms, including aryl group and substituted aryl group) or 5 to 2 carbon atoms together with R9
It may be substituted with any group selected from the atomic groups necessary to form a 7-membered ring (e.g. pyridine or piperidine group); R7 is an alkylene group containing 1 to 3 carbon atoms in the bonding group; (including substituted alkylene groups), or an alkylene group in which at least one methylene in said linking group is a dialkyl or diarylmethylene linking group, and preferably contains one carbon atom in the divalent linking group. , for example a methylene linkage group or a dialkyl-
or a diaryl-substituted methylene linking group; n is an integer of 1 or 2; R9 can be an aromatic group containing at least 5 atoms, preferably 5 to 20 atoms;
This also includes heterocyclic groups, such as groups containing a nucleus such as pyridine, tetrazole, benzimidazole, benzotriazole or isoquinoline, or carbocyclic arylene groups containing from 6 to 20 carbon atoms (preferably phenylene). phenylene groups and naphthylene groups substituted with groups or naphthylene groups). Furthermore, R9 is 1~
It may also be an aliphatic hydrocarbon group such as an alkylene group (including substituted alkylene groups) containing 12 carbon atoms. :
R8 is an alkyl group containing 1 to 40 carbon atoms (also including substituted alkyl groups and cycloalkyl groups), an aryl group containing 6 to 40 carbon atoms (including immediately aryl groups), or as defined above The substituent X1 may be,
Each of R6, R4 and R5 may be an atomic substituent such as a hydrogen atom or a halogen atom, but is preferably a polyatomic substituent such as an alkyl group containing 1 to 40 carbon atoms (
(including substituted alkyl groups and cycloalkyl groups); R6 and R5 or R4 and R5 together form a 5- to 7-membered ring with the rest of the molecule, including the di- or di-ring, if they are in adjacent positions on the ring If possible, each may be a substituent X1. However, R9
is an aliphatic hydrocarbon group such as an alkylene group, R6 and R4 must be polyatomic substituents, and R5 is preferably a polyatomic substituent, and Ql is an E
In the case of an electron-accepting antiphilic precursor group such as that defined for NuP, R4 or R adjacent to G1
The 6-substituent group can provide compounds with multiple groups that can be released by nucleophilic substitution.

Xl is given in at least one substituted position and X
Each of l and -(Q-R"-X3) is a ballasting group sufficiently large to render the compound immobile in the binder layer of the photographic element.
oup) or Xl and -(Q-R9-X3
) is a ballast group, the other is a ballast group, preferably a photographically useful group such as a photographic reagent, preferably a dye-providing substance such as an image dye or an image dye precursor. It is the basis. R7 is selected to make the nucleophilic group more accessible to E, allowing an intramolecular nucleophilic reaction with release of Q from E. Preferably, R7 is 3 to 3 between the atom that is the reaction center of the nucleophilic reaction of the nucleophilic group and the atom that is the reaction center of the electrophilic reaction of the electrophilic group.
selected to provide 5 atoms, whereby the compound has a 5- to 8-membered ring, more preferably a 5- to 6-membered ring, from the electrophilic group =(Q-R9- Xfl) can be formed by intramolecular nucleophilic substitution of a group.

Representative of this type of useful compounds are the following compounds IA-1-IA-9 and the like.

The following margins are left: R: The compound of the above general formula has improved overall image forming properties with improved Dmin and improved stability after processing, for example, when R8 is a Halky substituent that causes steric hindrance. can be shown. Representative groups that can serve as such R8 include cyclohexyl, isopropyl, isobutyl, and benzyl.

When R4, R5 and R6 contain a pallic substituent that provides steric hindrance to the adjacent portion of the quinone ring, improved imaging properties can also be obtained. Representative substituents include α- and β-substituted alkyl groups such as α-methylalkylcyclohexyl,
Includes isopyr, α-methylbenzyl, pt-butyl-α-phenethyl, and the like.

Although it may be more advantageous for this pulky substituent to be in compounds of the structure described above, they can also be used to occupy other analogous positions in the compound, thereby Gives improved photographic properties.

The compound represented by the general formula (IA) of the present invention can be synthesized, for example, by the method disclosed in JP-A-53-110827.

In certain preferred embodiments, the compound of the invention is a compound having the following general formula (IB).

General formula (IB> where ENuP is an electron-accepting precursor of a hydroxylamino group, such as nitroso (No), a stable nitroxyl group and preferably a nitro group (NO2); A is the remainder of the above general formula It is a group containing the atomic group necessary to form a 5- to 6-membered aromatic ring together with a polycyclic aromatic ring structure.

Here, the aromatic ring may be a carbocycle or a heterocycle, for example, a group containing an aromatic onium group in the ring, preferably A
represents a group necessary to form a carbocyclic ring such as a benzene ring or a naphthalene ring; W represents an electron-withdrawing group having a positive Hammett sigma value, such as nano, nido 1,1, fluoro, Includes groups or esters such as chlor'u, pro-7, iodo, 1-herinrus'-romethyl, trialkylammonium, carbonyl, N-substituted carbamoyl, sulfoxide, sulfonyl, N-substituted sulf-1 moyl, etc.: R12 is a hydrogen atom , i~; a substituted or unsubstituted alkyl group containing 30 carbon atoms; ``or a substituted or unsubstituted aryl group containing 6 to 30 carbon atoms; a valent organic group, such as an alkylene group, a mexaalkylene group, a thiaalkylenino group, an alkylene group, an alkyl- or aryl-substituted nitrogen group, and preferably at least one dialkyl group in the bonding group. - or diaryl- is an alkylene group containing substituted methylene: m and (L is a positive integer 1
or 2; p and r are positive integers of 1 or more, preferably p is 3 to 4, and ((R12)q -1-W
) is a substituent substituted on any part of the aromatic ring structure of A; E and Q provide an electrophilic cleavage group, where E is a reactive center for an electrophilic reaction, preferably thio Is it a carbonyl group including carbonyl (-C3-),
or a sulfonyl group. Q is a group that provides a monoatomic bond between E and Atom, more preferably 1 to 1
an amino group having an alkyl substituent containing 0 atoms, a substituted alkyl group, or an atomic group necessary to form a 5- to 7-membered ring together with QX2, such as a pyridine group or a piperidine group; n is 1 to 3; is an integer, preferably 1; Xl together with Q is an image dye-providing substance such as an image dye or an image dye precursor; Xl is a ballast-providing group as defined above, preferably is a substituted or unsubstituted alkyl group containing 8 to 30 carbon atoms, or 8
It is a substituted or unsubstituted aryl group containing ~30 carbon atoms (including the bonding group necessary for bonding to the aromatic ring). provided that at least one of Xi or R12 present in the compound is a group of sufficient size to render the compound of (IB) immobile and immobile in the alkali-permeable layer of the photographic element. That is, preferably at least one of Xl or RI2 contains 12 to 30 carbon atoms.

When multiple groups are present in the compound represented by the above formula, they may be the same or different. That is, p is 3 and each (RI2-W)- can be selected from a variety of different substituents specified.

The electron withdrawing groups mentioned for compounds of the above formula are:
a group with a positive Hammett sigma value, preferably a group with a sigma value greater than 0.2, or
Alternatively, as a substituent on an aromatic ring, a combination of more than 0.5 is an effective group. Hammett sigma value is 3
tericEffects in Organi
c Chemistry, John Wi
ley and Sons, Inc., 195
6. p, 570-574. and Progress in
Physical Organic Ch.
emistry, Vol. 2. 1nters
science p+, +bl 1shers,
1964, pp. 333-339.

Typical useful electron withdrawing groups with positive Hammett sigma values include cyano, nitro, fluoro, bromo1,
Includes iodine, 1-lifluoromethyl, trialgylammonium, carbonyl, N-substituted rubbermoyl, sulfoxide, sulfonyl, Nitrosulfamol, ester, and the like. electron-attracting (!aromatic ring with substituent)
As used herein, it refers to an onium compound in a ring, and also refers to a group substituted directly on the ring that can serve as a bonding group for another group, such as a ballast group.

The electron-withdrawing group contains in the ring the same group as in the compound of the following formula:

The compound represented by the general formula (IB) of the present invention can be synthesized by the method disclosed in JP-A-53-110827.

Next, specific examples of the compound represented by the general formula (IB) will be shown.

Margin below (IB-1) (IB-3) However, Ga4”: However, CoA2: However, CoA3 is 2, which is the same as in (IB-6).

J11'i However, Co114 is the same as in (IB-8).

However, COβ4 is d-dominant in the case of (IB-8).

However, Co/! 5: As a second example of the reducible dye releasing agent of the present invention, the general formula (
There is a compound represented by I[A) or (JIB).

(IIA) (n B) 141 Z-Y In the formula, each of (Nuox)' and (Nuoz)2 may be the same or different, and is an oxidized nucleophilic group such as a 〇- group or a HN- group. , Z represents a divalent group (e.g. sulfonyl group) which is electronegative to the carbon atoms carrying R14 and R15, and Y represents a group which becomes a mobile dye after being released together with the Z group. .

R11, R12 and R13 each represent a hydrogen atom, halogen, alkyl group, alkoxy group or acylamino group, R11 and R12 form a fused ring with the rest of the molecule when they are located adjacent to each other on the ring, and R14 and R15 each may be the same or different and represents hydrogen, a hydrocarbon group, or a substituted hydrocarbon, and RI 1 , R12, R13,
At least one of R14 and R15 contains a group that is large enough to prevent migration of the compound in the layer, ie, a diffusion-resistant group.

Diffusion-resistant residues are residues which allow the compounds according to the invention to be incorporated in a diffusion-resistant form in the hydrophilic colloids commonly used in photographic materials. generally carries straight or branched aliphatic groups, or generally has 8 carbon atoms
Organic residues capable of carrying carbocyclic or heterocyclic or aromatic groups having ˜20 are preferably used for this purpose. These residues can be attached directly or indirectly to the rest of the molecule, for example -NHCO-1-NH3O2-1-NR- (where R represents hydrogen or an alkyl group), -0-1-8
- or -5o2-.

The residues conferring resistance to diffusion further carry groups conferring solubility in water, such as sulfo groups or carboxyl groups, which may be present in anionic form.

But that's fine. Mobility is determined by the size of the compound's molecule as a whole, so in some cases, for example, if the molecule as a whole is large enough, it may have a group with a shorter chain length as a group that provides diffusion resistance. It is quite possible.

Compounds within the scope of general formulas (IIA) and (IIB), wherein (Nuox)1 and (Nucx)2 are nucleophilic groups (Nu)1 and (Nu)2, such as -CH- and -N
Compounds which have been reduced to H2 and methods for their synthesis are described in Helgie Patent No. 861,241, which claims priority with German Patent Application Box P26 54,213.

The preparation of the compounds represented by the above general formulas (IIA) and (IIB) is carried out by adding the corresponding reduced compounds, i.e., compounds having a nucleophilic group (Nu) in the non-oxidized state, in an excess of a solvent such as refluxing ethanol. This can be done by treatment with an oxidizing agent such as p-benzoquinone.

Other oxidizing agents suitable for use in the synthesis of compounds of general formulas (IIA) and (IIB) include methyl-1°4-benzoquinone, 2,5-dimethyl-1,4-penzoquinone, octyl-1. 1,4-benzoquinone, dodecyl-1,4
-benzoquinone, 2,3.5-trimethyl-1,4-benzoquinone, ■, 4-naphthoquinone, 2-methyl-1,
4-Nara-1 quinone, 2-octyl-1,4-naphthoquinone, 2-dodecyl-1,4-naphthoquinone, 5.8-methane-1,4-naphthoquinone, 9.10-0-benzo-
These include 1,4-naphthoquinone, 2,6-dimethyl-1°4-benzoquinone, and 2,6-dichloro-1,4-benzoquinone.

Methods for synthesizing compounds represented by general formulas (IIA) and (IIB) are described in JP-A-54-130927.

As specific examples of the compounds represented by (■A) and (nB) of the present invention, in addition to the compounds of the following ■-1, 111-1 to
Examples include oxidized products (compounds in which the hydroquinone moiety is oxidized to quinone) of the compounds listed in (1)-40.

Margin below ! 'i　　　n (I[I-14) (III-15) (III-18) p (In-19).

♂H1′1 1-1 11 H 65H5 (II[-31) (III-33) (m-35) (I[1-36> (I[l-40)] As the reducible dye releasing agent of the present invention , Japanese Patent Publication No. 53-11
No. 0828, German patent application (OLS) 3°008.58
Those listed in No. 8 are also valid.

As the oxidizable dye fixing agent of the present invention, JP-A-49-11
No. 1628, JP-A-51-63618, Re5ear
ch Disclosure 14447 (19
Also effective are the compounds described in U.S. Pat.

Quinone-type compounds used in the photographic material of the present invention (
nA) and (]IB) do not have dye-releasing ability as they are, and must obtain the ability to release hydrophilic dyes in a positive image-like manner by image-wise reduction in the unexposed areas caused by heating.

This makes storage and development more difficult compared to using photographic materials that initially contain the compound in reduced form as described in the aforementioned U.S. Pat. No. 3,980,479. This provides the advantage of considerably less fog formation.

Examples of the dye moiety contained in the compound of the present invention include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes,
Examples include groups such as carbonyl dyes, phthalocyanine dyes, and metal complex salts thereof.

Typical dye precursors contained in the compounds of the present invention are those that give dyes by hydrolysis, such as those disclosed in JP-A-48-125818 and U.S. Pat. No. 3,222.19.
As described in No. 6 and No. 3,307,947, examples include those in which the auxochrome of a dye is acylated (temporary short-wave dye). In this way, by temporarily shortening the absorption of the dye by acylation during the exposure period, when these color image forming agents are mixed with a light-sensitive emulsion and coated, the reduction due to light absorption can be reduced. You can prevent the feeling. Note that for this purpose, it is also possible to use a dye that has different hues when transferred onto the mordant and when present in the emulsion layer. The dye moiety can also have a group that provides water solubility, such as a carboxyl group or a sulfonamide group.

For the diffusion-resistant reducible dye release agent of the present invention: 1. It is necessary that it is immobilized in a hydrophilic or hydrophobic binder and that only the released dye has mobility.

2. It has excellent stability to heat and dye release aids, and does not release image-forming dyes until reduced.

3. Easy to synthesize.

The following characteristics are required.

Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes,
There are styryl dyes, 210 dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, etc., and representative examples are shown by hue. Note that these dyes can also be used in a form whose wavelength is temporarily shortened so that the color can be restored during development.

Yellowt I I2 In the above formula, R11 to RI[5 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group,
Acyl group, cyan group, hydroxyl group, alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group,
Aryloxyalkyl group, nitro group, halogen atom,
Sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group, N-substituted carbamoyl group, aryloxyalkyl group, amino group, substituted amino group, alkylthio group,
Represents a substituent selected from arylthio groups, and the alkyl and aryl groups in these substituents further include halogen atoms, hydroxyl groups, cyano groups, acyl groups, acylamino groups, alkoxy groups, carbamoyl groups, and substituted carbamoyl groups. , a sulfamoyl group, a substituted sulfamoyl group, a carboxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, or a ureido group.

In the present invention, an electron donor is used in combination with a reducible dye releasing agent such that exposure to light followed by thermal development results in imagewise release of a mobile hydrophilic dye.

That is, when the electron donor is heated, it undergoes a redox reaction with the exposed silver halide before reacting with the reducible dye-releasing agent, and is destroyed in an imagewise manner, and the remaining electron donor is It then reacts with a reducible dye-releasing agent. Thus, the reducible dye releasing agent is capable of releasing a hydrophilic mobile dye as an inverse function of the destruction of the electron donor. As used herein, the term "electron donor" refers to the nucleophilic breaker number of the reducible dye-releasing agent that reacts with the various reducible dye-releasing agents contained in the photographic element. It means a compound that can transfer electrons to a group.

The electron donor must have a reaction rate with the exposed /S silver halide that is faster than the rate of reaction with the reducible dye releasing agent. Preferably, it is evaluated by the redox half-life time (hereinafter referred to as redox tl/2),
The rate of reaction between the electron donor and the silver halide is at least 5 times, preferably 10 times or more, the rate of reaction between the electron donor and the reducible dye releasing agent, in which case the mobile component is imagewise selected. released. Such electron donors include ascorbic acid, trihydroxypyrimidines, e.g.
2-methyl-4,5,6-)lihydroxypyrimidine and hydroxylamines such as diethylhydroxylamine.

In certain preferred examples, an electron donor is used in combination with an electron transfer agent (referred to herein as ETA). Generally, ETA is a compound that is a much better silver halide developer than the electron donor under processing conditions, and where the electron donor is unable to develop the silver halide or its intended purpose. ETA functions to develop the silver halide to provide a corresponding image-like pattern of destroyed electron donors. This is because oxidized ETA readily accepts electrons from electron donors. Generally, when using a combination of an electron donor and a useful ETA, the ET
Under the same processing conditions, it provides a faster development rate for silver halide than if only the electron donor was used in processing without A. In a highly preferred example, E
TA together with reducible dye releasing agents slow redox t1/
2, which is at least slower than the redox t1/2 of the electron donor used with the reducible dye releasing agent, preferably at least 10 times slower; this example shows a high While allowing flexibility, it provides the freedom to obtain optimal release rates when using reducible dye release agents.

Typical ETA compounds useful from this point of view include hydroquinone compounds such as hydroquinone, 2,5-dichlorohydroquinone and 2-chlorohydroquinone; aminophenol compounds such as:
4-aminophenol, N-methylaminophenol,
3-methyl-4-aminophenol and 3,5-dibromoaminophenol; catechol compounds such as catechol, 4-cyclohexylcatechol, 3-methoxycatechol and 4-(N-octadecylamino)catechol; phenylenediamine compounds such as N , N-diethyl-p-phenylenediamine, 3-methyl-N, N-diethyl-p-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine and N,
N, N'.

There is No-tetramethyl-p-phenylenediamine. In particularly preferred examples, ETA is a 3-pyrazolidone compound, such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3- Pyrazolidone; l-m-tolyl-3-pyrazolidone, 1-p-
1-true 3-pyrazolidone, ■-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3
-pyrazolidone, 1-phenyl-4,4-bis-(hydroxymethyl)-3-pyrazolidone, 1°4-dimethyl-3-pyrazolidone, 4-methyl-3-pyrazolidone,
4.4-dimethyl-3-bira'/'IJFn, 1-(3
-chlorophenyl)-4-methyl-3-pyrazolidone,
1-(4-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(3-chlorophenyl)-3-pyrazolidone, ■-(4-chlorophenyl)-3-pyrazolidone,
1-(4-)lyl)-4-methyl-3-pyrazolidone,
1-(2-1-lyl)-4-methyl-3-pyrazolidone, 1-(4-)lyl)-3-pyrazolidone, 1-(3-
) lyl)-3-pyrazolidone, ■-(3-1-lyl-
4,4-dimethyl-3-pyrazolidone, 1- (2-1
4-dimethyl-3-pyrazolidone and 5-methyl-3-pyrazolidone. U.S. Patent No. 3. Combinations of various ETAs can also be used, such as those disclosed in No. 039.869. Although such developing agents can be used in liquid processing compositions, they can also be included at least in part in any one or more layers of a photographic element or film unit. For example, they can be used in silver halide emulsion layers, in dye image-providing materials, in interlayers, and in image-receiving layers. Of course, what kind of ETA to choose depends on the process,
It depends on what electron donors and reducible dye-releasing agents are used, and what photographic elements are processed and under what conditions.

In the photographic elements of this invention, the reducible dye releasing agent of this invention is preferably used in conjunction with an electron donor.

In multicolor photographic elements having separate yellow, magenta and cyan image dye-providing layer units, it is preferred to use a scavenger in the interlayer separating each layer unit to prevent color mixing. To reduce color mixing, suitable scavengers for mobile or partially mobile compounds in oxidized or reduced form can be used.

In one preferred example, effective separation can be achieved by including partially or completely a ballasted electron donor in the layer unit 1-. Interlayer diffusion is effectively reduced when a substantially immobile electron donor is used.

However, the compound remains active in the layer unit and transfers electrons to the reducible dye-releasing compound in close contact with it.

Once the imaging process is substantially complete, the migration of small amounts of electron donor to adjacent layer units does not have a substantially deleterious effect on the image.

When a very high degree of image texture is required (eg, multicolor photographic elements), thermally decomposable electron donor precursors are used in combination with the respective reducible dye-releasing compounds. In general, the decomposition of an electron donor precursor to an electron donor occurs at a finite rate;
The generated electron donor immediately reacts with the oxidized form of the electron transfer agent (ETA) generated during the silver halide development reaction or with developable silver halide.

In this reaction system, the ETA is regenerated so that more silver halide can be developed, and where development is occurring, electron donors are generated as quickly as each is produced by decomposition. has been destroyed. In this way, the reason why the electron donor generated by decomposition does not react with the reducible dye-releasing agent is that it exists effectively only in the non-active region (1), and is movable in the bulk. Releases photographically useful groups, such as mobile image dyes.Most preferably, a heat-decomposable electron donor precursor, especially when used in a multicolor photographic element, substantially Contains sufficient pallast groups to make it immobile.

When an electron donor precursor is used that can be decomposed by heating, the rate of decomposition of the electron donor precursor to the electron donor is determined with respect to the release of the mobile photographically useful group from the reducible dye releasing agent. Can be used for speed adjustment. This rate of decomposition can have an effect on the development rate of the silver halide, especially when small amounts of ETA are used. Therefore, as a redox t1/2 when used with these precursors that can be decomposed by heating, that is, reducible dye releasing agents, ETA
Those that give a redox t1/2 longer than the redox t1/2 when used together, for example, those that give a redox t1/2 longer than the redox t1/2 when used together, for example, those that are longer than 5 seconds, preferably longer than 10 seconds for each reducible dye releasing agent, are generally used.

It should be appreciated that the rate of cross-oxidation of the electron donor and the reducible dye-releasing compound can be utilized for control steps in the release of photographically useful groups.

The electron donor is generally present in the photographic element in a ratio of electron donor to reducible dye releasing agent of 1:2 to 6:1, preferably 1:1.
A ratio of ~2:1 is used.

In one preferred example, the electron donor precursor that can be decomposed upon heating has the formula:

R3+ Here, A represents a group containing the necessary atomic group to form an aromatic ring of 5 to 6 atoms together with the rest of the above formula, and is preferably a carbocyclic aromatic ring, and R30 is a hydrogen atom or,
One or more groups containing from 1 to 3 carbon atoms, preferably of sufficient size to render the compound immobile in the binder layer of the photographic element, such as from 8 to 30 carbon atoms. ,N-substituted carba% iJl/
Group Example 7L includes N-alkylcarbamoyl, alkylthioether group, N-substituted sulfamoyl group such as N-furkylsulfamoyl, alkoxycarbonyl group, and R31 is [substituted or substituted containing ~30 carbon atoms] or 6 to 30+7[i
A substituted or unsubstituted aryl group containing an atom is preferably a methyl group. Typical useful compounds within the scope of this formula include: In other examples, other electron donors that are decomposable upon heating can be used. For example, D-10 D-14 In yet another example, the electron donor can be present in the keto form. For example, in the form of protohydroquinone, which is enolized in a base to form an electron donor. Compounds of this type are:

ED-15 In yet another example, it is preferred that the precursor is not a precursor, but is at least semi-immobile in the layers of the photographic element. Typical compounds of this type are as follows.

ED-16 ED-17 In yet another example, ED-23 If the above electron donor precursor is salty when heated, it is advantageous in that it decomposes by heating at a low temperature of −1.

The reducible dye-releasing agent of the present invention and the electrolyte 4P used for IJ
, as a given matter, number, jl, in addition to the above ED-1-LD-23, Okoku Special Fraud No. 4,263,393, same No. 11.278
, No. 750, German Patent Application (OLS) No. 3. oot;,
The one described in No. 268 is also 2JJ.

The reducible dye releasing agent of the present invention is disclosed in U.S. Pat.
．． It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid algyl eno, thiol (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (shisoenyl phosphene-1, trisoenylphosphere I,
, tricresyl sulfate, dioctyl phthyl phosphate), citric acid esters (e.g. acetyl citrate)
1F riftilun, benzoic acid ester (octyl benzoate), alkyl amide (e.g. diethyl lauryl amide)
, fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesate esters (e.g. tributyl trimesate), or organic solvents with a boiling point of 30°C to 160°C, such as ethyl acetate, lower alkyl acetates such as butyl acetate,
After dissolving in ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Special Publication No. 51-39853, Japanese Patent Publication No. 51-59943
The dispersion method using polymers described in No.

In addition, various surfactants can be used when dispersing the reducible dye-releasing agent in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. can use things.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less, based on the reducible dye releasing agent 186 used.

Silver halides used in the present invention include silver chloride, silver chlorobromide, 1. Silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, silver iodide, etc.

In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, it is preferable to use silver halide containing silver iodide crystals in a portion of each grain. Such silver halide exhibits a pattern of pure silver iodide as its XIJ1 diffraction pattern.

Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary halide emulsions, the silver halide grains form perfect crystals. For example, when measuring X-ray diffraction of a silver iodobromide emulsion, no pattern of silver iodide crystals or silver bromide crystals appears, but an X-ray diffraction pattern appears at positions corresponding to the mixing ratio.

In the present invention, particularly preferred silver halides are silver chloroiodide, silver iodobromide, and silver chloroiodobromide, which contain silver iodide crystals in their grains and therefore exhibit an X-ray pattern of silver iodide crystals. .

Such silver halide, for example silver iodobromide, can be obtained by first adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding potassium iodide.

Two or more types of silver halides having different sizes and/or halogen compositions may be used in combination.

The grain size of the silver halide used in the present invention has an average grain size of 0.001. 10 from t+m. +rm, preferably o, ooi μm to 5 μm.

The silver halide used in the present invention may be used as it is, but it may also be compounded with chemical sensitizers such as compounds such as sulfur, selenium, tellurium, etc., compounds such as gold, platinum, palladium, rhodium and iridium, and halogenated silver halide. Chemical sensitization may also be achieved by the use of reducing agents such as tin or combinations thereof. For more information,
“The Theory of the Photo
o-graphic Process'' 4th edition, T.

H. James, Chapter 5, pages 149-169.

In a particularly preferred embodiment of the present invention, an organic silver salt oxidizing agent is used in combination, but the silver halide used in this case is characterized by containing pure silver iodide crystals when silver halide is used alone. All silver halides known in the art can be used.

The organic silver salt oxidizing agent used in the present invention is preferably used at a temperature of 80° C. or higher in the presence of photosensitive silver halide, preferably at a temperature of 100° C.
When heated above ℃, reacts with the image-forming substance or a reducing agent coexisting with the image-forming substance if necessary,
It forms a silver image.

By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color with higher density.

Examples of such organic silver salt oxidizing agents include silver salts of organic compounds having a carboxyl group, and typical examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. There is.

Examples of aliphatic carboxylic acids include silver behenic acid, silver stearic acid, silver oleic acid, silver lauric acid, silver capric acid, silver myristic acid, and silver palmitic acid. , silver salt of maleic acid, silver salt of fumaric acid, silver salt of tartaric acid, silver salt of furoic acid, silver salt of linoleic acid, silver salt of oleic acid, silver salt of adipic acid, silver salt of sebacic acid, succinic acid. Silver salt of , silver salt of acetic acid, silver salt of arsenic acid 1. There are silver salts of camphoric acid, etc. Also, silver salts substituted with halogen atoms or hydroxyl groups are also effective.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of benzoic acid, silver salts of 3゜5-dihydroxybenzoic acid, silver salts of 0-methylbenzoic acid, and silver salts of m-methylbenzoic acid. , silver salt of p-methylbenzoic acid, 2.
Silver salts of substituted benzoic acids such as silver salts of 4-dichlorobenzoic acid, silver salts of acetamidobenzoic acid, silver salts of p-phenylbenzoic acid, silver salts of gallic acid, silver salts of tannic acid, and silver salts of phthalic acid. Silver salts, silver salts of terephthalic acid, silver salts of salicylic acid, silver salts of phenylacetic acid, silver salts of pyromellitic acid, 3-carpoxy/methino ζ 4- as described in U.S. Pat. A silver salt of methyl-4-thiasolini/-2-thiomethyl is described in U.S. Pat. be.

others! There are silver salts of compounds and derivatives thereof having a -5 mercap 1- group or a thione group.

Example ni,,ge 3-mercapto-4-)l-1゜2
．． Silver salt of 4-triazole, Silver salt of 2-mercap[・benzimidazole, Silver salt of 2-mercapto-5-amino, notiacyazole, Silver salt of 2-mercap 1-benzthiazole, 2-(S- Silver salt of benzthiazole (ethyl glycolamide), S-alkyl (12-22 carbon atoms)
alkyl group) thioglycol acetic acid, etc.,
Silver salts of dithiocarboxylic acids such as silver salts of thioglycolic acid and silver salts of dithioacetic acid described in No. 2822i, silver salts of dithioamide, and 5-carboxy-1-methyl-2-phenyl-4-thiopyridine. silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, silver salt of mercaptooxadiazole, U.S. Pat. No. 4,12
3,274, such as the 1,2,4-mercap 1-triazole derivative 3-amino-5-
Silver salt of pendylthio 1,2°4-(.lyazole, 3-(2-carboxyethyl)-4-methyl-4-thianrin-2- as described in U.S. Pat. No. 3,801.678
It is a silver salt of a thione compound such as a silver salt of thione.

In addition, there are silver salts of compounds having imino groups. For example, Special Publication No. 44-30270 1. Silver salts of benzotriazole and its derivatives as described in Publication No. 45-18416,
For example, a silver salt of benzotriazole, a silver salt of an alkyl-substituted benzotriazole such as a silver salt of methylhencytriazole, a silver salt of a halogen-substituted benzotriazole such as a silver salt of 5-chlorobenzotriazole, a silver salt of butylcarboimidohencytriazole. Silver salts of carbimidobenzotriazoles such as, U.S. Pat. No. 4,220.709
1 described in the specification of the No. 2. 4-) Riazole and 1-H
- Silver salts of tetrazole, silver salts of carbazole, silver salts of saccharin, silver salts of imidazole and imidazole derivatives, etc.

In addition, in the present invention, Research Disclosure Vol. 1.17 (1, No. 17029, June 1978)
, The organic metal salts such as silver salts and copper stearate described above can also be used in the various types mentioned above! ! It can be used in the same way as salt. Two or more types of organic silver salt oxidizing agents can be used in combination.

In the present invention, a reducing agent can be used as necessary. The reducing agent in this case is an auxiliary developer,
Oxidized by a silver halide and/or organic silver salt oxidizing agent, the oxidized product is no longer able to reduce the reducible dye-releasing agent, but contributes to the reduction of the reducible dye-releasing agent in the unfinished area. It is a compound that can

Useful auxiliary developers include alkyl-substituted hydroquinones such as octa-f-rI quinone, t-butylhydroquinone, and 2,5-dimethylhydroquinone, catechols, pyrogallols, herokene-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, Hydroquinones, alkoxy-substituted hydroquinones such as methoxyhydroquinone,
There are polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N,N'-c(2-ethoxyethyl)hydroxylamine, ■-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1 -Phenyl-3-pyrazolidone and other birasolitons, reductones, hydroxytetronic acids, and the like are useful.

Auxiliary developers can be used in a range of concentrations. Useful concentration ranges are o,'oo for silver.

Particularly useful concentration ranges are 5 times molar to 20 times molar.
o, ooi times the mole to 4 times the mole.

Although the thermal development process during heating of the present invention is not fully clear, it can be considered as follows.

When a photosensitive material is irradiated with light, a latent image is formed on the photosensitive silver halide. Regarding this, T.H.
The Theory of the Ph
otographicprocess″3rd Ed
tion, pages 105 to 148.

Furthermore, by heating the photosensitive material, an oxidation-reduction reaction occurs between the exposed photosensitive silver halide and the reducing electron transfer agent and/or electron donor, and a silver image is generated in the exposed area. The transfer agent and/or electron donor is oxidized.

On the other hand, in the unexposed area, due to heating, the reducible dye-releasing agent reacts with the remaining electron transfer agent and/or electron donor as an inverse function to the silver image, and is reduced to a reduced form. The reduced reducible dye-releasing agent is cleaved to release the dye. In this case, the coexistence of a nucleophilic reagent promotes the dye release reaction. When an organic silver salt oxidizing agent is used in combination, it is necessary that the silver halide and the organic silver salt oxidizing agent exist at a substantially effective distance in order to promptly initiate the reaction. It is desirable that the silver halide and the organic silver salt oxidizing agent exist in the same layer.

Development by heating differs from so-called wet development in that the reaction requires time because the diffusion of reactive molecular species is restricted. However, if too much time is spent on heating for development, the thermal reaction in the unexposed areas cannot be ignored and so-called fog occurs, which is undesirable.

In the present invention, a hot solvent can be used as one means for improving such disadvantages.

Here, "B solvent" refers to a non-hydrolyzable solvent that is solid at ambient temperature but exhibits a mixed melting point with other components at a temperature of 1 degree or less during the heat treatment used. It refers to organic feed, and when heat-developed in the presence of a hot solvent, the development speed can be accelerated and image quality can be improved. Such thermal solvents used in the present invention include compounds that can serve as solvents for developing agents, compounds with high dielectric constants that are known to accelerate the physical development of silver salts, etc. It is for use. Useful thermal solvents include:
Polyglycols described in U.S. Pat. No. 3,347.675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as oleate ester, beeswax, monostearin, -5
High dielectric constant compounds having o2-1-CO- groups, such as acetamide, succinimide, ethyl carbamate,
Urea, methylsulfonamide, ethylene carbonate, polar substance described in US Pat. No. a, ej7.9s9, 4
-Lactone of hydroxybutanoic acid, methylsulfinylmethaneophene-1,1-dioxide, 1,10-decanediol described in Research Disclosure magazine, December 1976, pages 26-28, methyl anisate, biphenyl perate, etc. is preferably used.

Although the role of the thermal solvent in the present invention is not necessarily clear, it is understood that its main role is to promote the diffusion of reactive molecular species during development.

The photosensitive silver halide, organic silver salt oxidizing agent of the present invention is prepared in the following binder. A reducible dye-releasing agent is also dispersed in the binder described below.

The binders used in the present invention can be used alone or in combination. This binder has
Hydrophilic materials can be used. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, and natural polymers such as starch, gum arabic, pullulan, and dextrin. and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinyl alcohol, 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 silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. For these dyes, any of the basic heterocyclic nuclei commonly used for cyanine dyes can be used. That is. Pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these nuclei A nucleus in which an aromatic hydrocarbon ring is fused to, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadole nucleus, a tufted oxazole nucleus,
＼Zothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes have a core with a ketomethylone structure and j-, pyrazoline-5
-Apply 5- to 6-membered heterocyclic nuclei such as ion nucleus, 1,000-tonin nucleus, 2-thioxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. be able to.

Useful sensitizing dyes include, for example, F=(TS Patent No. 9'
2'. No. 9,080, U.S. Patent No. 2.234,
No. 658, same No. 2. , No. 493.748, Inter 2,50
No. 3,776, No. 2.519,001, No. 2, 9
No. 12,329, No. 3.6'56,959, No. 3
, No. 672, 897, No. 3,694.

No. 217, No. 4.025.349, No. 4.

No. 046,572, British Patent No. 1.242,588;
Examples include those described in Japanese Patent Publication No. 44-1 4030 and Japanese Patent Publication No. 52-24844.

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

Representative examples are U.S. Patent No. 2,688.545 and U.S. Pat.
．． 977, 229, 3,397.060, 3,522,052, 1 No. 3,527.641,
Same No. 3,617,293, Same No. 3,628,964, Same No. 3. 666, 480, same No. 3,672,8
No. 98, No. 3,679.428, No. 3,703,
No. 377, No. 3,769,301, No. 3,814
, No. 609, No. 3,837,862, No. 4,02
6°707, British Patent No. 1,344.281, British Patent No. 1. ．． No. 507,803, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Application Publication No. 110618/1982, and Japanese Patent Publication No. 52-109925.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with a nitrogen-containing heterocyclic group (eg, U.S. Pat. No. 2,933.3901, U.S. Pat. No. 3.635.
7'21), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510)1. It may also contain cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, U.S. Patent No. 3.615,641, U.S. Patent No. 3.617°295,
The combination described in No. 3,635,721 is particularly useful.

In the present invention, various dye release aids are used in various ways,
For example, it can be used by being included in any layer of a photosensitive material or any layer of a dye fixing material. A dye-releasing agent is a reducible dye-releasing agent that promotes the redox reaction between an electron transfer agent and/or an electron donor and a reducible dye-releasing agent, or is oxidized in a subsequent dye-releasing reaction. In addition, a base or a base precursor is used as a substance capable of acting nucleophilically to promote dye release. In the present invention, it is particularly advantageous to use these dye-releasing aids in order to accelerate the reaction, but when these dye-releasing aids are incorporated into the light-sensitive material, they must be of a color that does not impair the storage stability of the light-sensitive material. 2 Examples of preferred bases that can be used in photosensitive materials include amines, including trialkylamines, hydroxylamines, aliphatic polyamines,
Mention may be made of N-alkylff1l aromatic amines, N-hydroxyalkyl substituted aromatic amines, and bis(p-(dialkylamino)phenylcomethanes).
Ru. Also, U.S. Patent No. 2,410,64.4 has No. J, betaine tetramethylammonium iodide, diaminobutane dihydrochloride, and U.S. Pat. No. 3,506,444.
In this issue, organic compounds containing amino acids such as urea and 6-aminocarboxylic acid are described and are useful.

The base precursor releases a basic component when heated. An example of a typical base precursor is British Patent No. 998,9.
It is described in No. 49. Preferred A7 base precursors are salts of carboxylic acids and organic bases; useful carboxylic acids include triphanic coloacetic acid and trifluoroacetic acid; useful bases include guanidine, piperidine, morpholine, p-toluidine, and 2-pyrine. They are equally powerful. U.S. Patent Nos. 3 and 2
2 (Guanidine trichloroacetic acid described in No. 1,846 is particularly useful. Also, the aldonamides described in JP-A No. 50-22625 decompose at high temperature to produce a base, and are preferably used. .

These dye release aids can be used in a wide variety of ways. A useful range is 50% by weight or less, preferably 0.01% to 4% by weight of the coated dry film of the photosensitive material.
It is in the range of 0% by weight.

In the heat-developable light-sensitive material of the present invention, it is particularly 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, A'1. , A2, A:5. , A4 may be the same or different, and each represents a substituent selected from a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group, and a heterocyclic residue. Alternatively, A1 and A2 or A3 and A4 may be linked to form a ring.

Specific examples include H2N5.02NH2, H2N5ONN (CI■3)2, H2N5o2N(C2H5)2,
II7・N S O2N HCH3, H2N S 02
N <C2H40H)2, C143N HS O2N
Examples include HC113 and 2112.

The above compounds can be used in a wide range of applications.

A useful range is 20% by weight or less, more preferably 0.1 to 15% by weight of the coated dry film of the photosensitive material.

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

A water-releasing compound is a compound that decomposes and releases water during thermal development. These compounds are particularly known for transfer printing of fibers, and NH4F6 (SC+4)2.12) (70) described in JP-A-50-88306 is useful.

The support for the photosensitive material used in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinyl acecool film, polystyrene film, polycarbonate film, and polyethylene terrestrial film. and films or resin materials related thereto. U.S. Patent No. 3.634
．． The polyesters described in No. 089 and No. 3.725.070 are preferably used. Particularly preferably, polyethylene terephthalate I film is used.

The coating solution used in the present invention can be prepared by mixing separately formed silver halide and organometallic salt oxidizing agent before use; Mixing in a ball mill for a long time is also effective.

Also effective is a method in which a halogen-containing compound is added to a prepared organic silver salt oxidizing agent to form halogen silver with the silver in the organic silver salt oxidizing agent.

For information on how to make these silver halides and organic silver salt oxidizing agents, how to mix them, etc., see Ri-chi Disclosure No. 170.29, JP-A-50-32928, JP-A No. 51-42529, It is described in U.S. Pat.

In the present invention, the coating amount of the photosensitive silver halide and organic silver salt oxidizing agent is 50 mg to 10 g in total in terms of silver.
m2 is appropriate.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic agents, slippery improvement, emulsification dispersion,
Prevention of adhesion and improvement of photographic properties (e.g. development acceleration, contrast enhancement,
Various surfactants may be included for various purposes such as sensitization).

For example, Ribonin (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, (Alkylene glycol alkyl amine or Ami F, silicone polyethylene oxide adducts) 4. Nonionic surfactants such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkyl phenates, norpolyglycerides) fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates 1. Alkylbenzene sulfonates, markylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, ~ poly Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups such as oxyethylene alkyl phosphates; amino acids, aminoal; torsulfonic acids, aminoalkyl sulfates Or amphoteric surfactants such as phosphoric acid esters, alkyl petamines, amine oxides, etc.; alkylamine salts, aliphatic or aromatic quaternary salts, complex compounds such as pyridinium, imidazolium, etc.! ! @4th grade ammonium,
? , salt cheek, and aliphatic or heterocyclic ring] Tosboniu A
Alternatively, cationic surfactants such as Ruhoniu J, salts, etc. can be used.

Among the above-mentioned surfactants, a poly, ethylene glycol type nonionic surfactant having a repeating center of ethyl oxide in the molecule is included in the photosensitive material6.
Talented and desirable. Particularly preferred is a repeating unit of ethylene oxide of 5J27. It is desirable that the value be f.

Ionic surfactants that do not meet the above conditions are widely used in applications other than 1p7, and their structures, properties, and synthesis methods are well known. Representative known documents include 5urfact; Int'5science 3er
ies Volume, Nontonic
5urfactants (Edited by
Mart, in JShick, Marcel
Dekker Inc., 1967), 5u
rfaceActfve Ethylene
Oy, 1de Adduces (SchoufaIdt
,・N Pergamon Press 1969
), and the nonionic surfactants described in these documents that satisfy 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 W surfactant is used in an amount equal to ff1JifJ2J, preferably 50% or less, relative to the hydrophilic binder.

The photosensitive material of the present invention can contain 1L containing a cationic compound having a pyridinium source. An example of a cationic compound having a pyridinium group is PSA, 1ou
rnal, 5ect ioo B36 (1953
), USP2. 648. 604, υSP3,671
, 247, Special Publication No. 44-30074, Special Publication No. 44-95
03 etc.

In the light-sensitive material used in the present invention, a compound that activates development and simultaneously stabilizes the image can be used. Among them, isothiuroniums represented by 2-hydroxyethyl isothiuronium and trichloroacetate described in U.S. Patent No. 3,301,678, and U.S. Patent No. 3,66
Bisisothiuroniums such as 1,8-(3,6-thioxaoctane)bis(intiuronium trifluoroacetate) described in No. 9,670, West German Patent No. 2゜162
．． Thiform compounds described in publication No. 714, U.S. Patent No. 4,
Thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-7minor 5-bromoethyl-2-thiazolium trichloroacetate described in No. 012.260, bis( Compounds having α-sulfonylacetate as an acidic moiety, such as 2-amino-2-thiazolium)methylenebis(sulfonylacetate), 2-amino-2-thiazoliumphenylsulfonylacetate, etc.
Compounds having 2-carboxycarboxamide as the acidic moiety described in US Pat. No. 4,088,496 are preferably used.

In the case of the present invention, since the reducible dye-releasing agent is colored, it is not so necessary to further contain anti-irradiation, anti-halation substances, or various dyes in the light-sensitive material, but the In order to improve sharpness, Japanese Patent Publication No. 48-3692, U.S. Patent No. 3,25
No. 3,921, No. 2.527,583, No. 2.
956. Filter dyes, absorbent substances, etc. described in various specifications such as No. 879 can be contained.

These dyes are preferably heat-decolorizable, such as those described in U.S. Pat. Nos. 3,769,019 and 3.745.
Preference is given to dyes such as those described in US Pat. No. 3,615,432.

The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials, layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, A
It can contain an H layer, a release layer, etc. Various additives include Research Disclosure Vow, 17
0. No. of June 1978: Additives described in No. 17029, such as plasticizers, sharpness improving dyes, AH dyes, enhancing dyes, capping agents, surfactants, and fluorescent whitening agents. There are additives such as anti-fading agents.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, go-coating layer, backing layer, and other dark layers are prepared using the dipping method, air knife method, curtain coating method, or U.S. A light-sensitive material can be prepared by sequentially coating onto a support using various coating methods, such as the hopper coating method described in Japanese Patent No. 3,681.294, and drying.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837.095.

In the present invention, the latent image obtained after exposure of the photosensitive material is maintained at a moderately elevated temperature, such as from about 0°C to about 250°C, for about 0.5 seconds to about 300 seconds. The image can be developed by heating the entire image. As long as the temperature is within the above range, it can be used at either high or low temperatures by increasing or shortening the heating time.

A temperature range of about 10°C to about 160°C is particularly useful.

As the heating means, a heating element using a simple hot plate, an iron, a hot roller, a carboxylic powder, a chikun white, etc.
Ordinary means such as a method using a similar method can be used.

In the image forming method of the present invention in which an image formed by a mobile hydrophilic dye is moved from a dye fixing layer to a dye fixing layer under a high temperature condition in the presence of a hydrophilic thermal solvent, the movement of the mobile dye starts at the same time as the release of the dye. or after the release of the dye is completed. Therefore, heating for transfer may be performed after heat development or at the same time as 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.

The heating temperature of the dye transfer reservoir is 60°C to 250°C from the viewpoint of storage stability and workability of the photosensitive material. You can choose what works best for you. Of course, it is necessary for hydrophilic thermal solvents to help the dye transfer quickly when heated, but it is also necessary to consider the heat resistance of the photosensitive material, etc. The required melting point is between 40°C and 250°C, preferably between 40°C and 250°C.
00°C, more preferably 40°C to 150°C.

In the present invention, a "hydrophilic thermal solvent" is a compound that is solid at room temperature but becomes liquid when heated, and has an (inorganic/organic) value of 1 and 12. It is defined as a compound whose solubility in water is one level higher than that in water. Area of chemistry 11
719 (1957).

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

- In general, it is known from experience that the preferred solvent for dissolving organic compounds is that the (inorganic/organic) value of the solvent is close to the (inorganic/organic) value of the organic compound. . On the other hand, (
The (inorganic/organic) value of the hydrophilic dye is around 1, and the (inorganic/organic) value of the hydrophilic dye is higher than that of the stiff reducible dye releasing agent. agent (inorganic/
organic) has a value larger than the value, preferably L<is],
It has a value of 5 or more, particularly preferably 2 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 reducible dye release agent. It needs to be greater than the (inorganic/organic) value of the releasing agent. That is, as a hydrophilic thermal solvent, it is an essential condition that the (inorganic/organic) value is 1 or more, preferably 2 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 100 or less.

The hydrophilic hot solvent of the present invention only needs to be able to substantially assist the movement of the hydrophilic dye in the dye fixing layer caused by heat development, so it can not only be included in the dye fixing layer. 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 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 its adjacent layer.

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.

The hydrophilic thermal mixture used in the present invention is a photosensitive material and/or
'or 5.~500% by weight of dye fixing materials,
It can be used at a coating rate of kF, <LJ, 20 to 200ifif9i, particularly preferably 30 to 150%.

Examples of the hydrophilic compounds used in the present invention include ureas, pyridines, chi 1 ton, surbo, Noah\de cheek, imi 1-, alcohols, oxime yi, and other complex yi.
I can raise my cheeks.

Next, specific examples of the aqueous hot solvent used in the present invention will be shown.

Margin below (8) 0 1 1 (2NCNHC2H40H 1 (Jl) (12) (34) (35) CI (3S O2NH2,,) 100F17 b',
, +2 r411 z (36) (37
) 82NS02NH2,3HCNH3O2N)! 2 (38
) (39) (40) (41) (44) (47) IOCH2(CHOH)3CH70H.

(411) (49)C,
H,5C(CH20ID 3, C2H7C(Cj(
20H) 3 (50) (51)
02NG (Chzoll) 3, Sorbit (5
2) (53)(54) 1701-;ji2-r7H=cfl-1:H20H
(55) (56) CH3CH=NOIL HON=CHCH=NOH(
59n (6o) (61)
(62) Among these, ureas (1), (2), (3), (
, 10), pyridines (17>, (19), amides (26), (30), (33), sulfonamides (34), (36), imides (40), ( 41
), (43), (44) and alcohol (46),
(54) is particularly preferred. Further, the hydrophilic heat solvent used in the present invention can be used alone or in combination of two or more.

In the present invention, the hydrophilic mobile dye generated in an imagewise manner is moved by heat development simultaneously with imagewise exposure or subsequent to imagewise exposure, and the rTJ mobile dye of 122 is stopped to form a dye image. A dye fixing layer is required to fix the dye. For this purpose, the photosensitive material of the present invention has a photosensitive layer (1) containing at least silver halide, a reducible dye-releasing agent, a binder and, if necessary, an organic silver salting agent, on a supporting body; It is composed of a dye fixing layer (II) that can receive and stop the hydrophilic and mobile dye formed in the layer T).In this way, one photosensitive layer (1) and the dye fixing layer (II) are combined. may be formed on the same support or on separate supports.The dye fixing layer (n) and the photosensitive Jtf (1
) can also be used separately. For example, the photosensitive layer can be peeled off with the dye fixing M(■)5 after imagewise photouniform and heat development.

In addition, when the photosensitive material in which the photosensitive layer (N) is spread on a support and the fixing material in which the fixing layer (II) is coated on the support are formed separately, the photosensitive material is imagewise exposed. After uniformity and heating, the fixing material can be layered to transfer the mobile dye to the fixing layer (■). Alternatively, there is a method in which a photosensitive material is imagewise exposed, and then the dye fixing layer (n) is placed together and heated uniformly.

With photosensitive materials! For example, for adhesion to the three fixed materials,
T,! Although it is possible to use the usual 7i''tf= such as those made by -1-ra, in order to ensure sufficient adhesion, heating can also be applied at the time of adhesion (every 1.yJ l).

After image exposure, or (8! After heat development at the same time as exposure, if the surface of the light-sensitive material is brought into close contact with the dye-receiving surface of the dye-fixing and +4 dyes and heated 1. Of,?j
From this point of view, the heating temperature and heating time can be set independently of the heating for development.

When this method is adopted, it is preferable that the heating for development completes the reaction for development within a short period of time so as not to contribute to dye migration as much as possible, while at the same time allowing the dye to be released in an imagewise manner. In order to obtain a clear image, it is preferable to keep the heating for transferring the dye to the dye transfer layer as low as possible within an appropriate transfer time range so as not to cause a thermal reaction in the unexposed area.

The dye-fixed FJ (n) may include a white reflective layer. For example, a layer of titanium dioxide dispersed in gelatin can be provided on a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer and the transfer color is 1m.
@! By viewing from the transparent support side, a reflective color image can be obtained.

A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer. As the dye transfer aid, water or a basic aqueous solution containing caustic acid, caustic potash, or an inorganic alkali metal salt is used.

Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, 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 layer with a solvent, or it may be incorporated into the material as crystal water, water, etc.

Dye fixation includes 11 color A mordants for dye fixation, hydrophilic heat solvents to help transfer the dye, bases and/or base precursors to promote dye release reactions, etc., and 1. Without combining τ, 1 MU et al., it is possible to create ・'-, which includes Ritame's Ba Ingu. When the dye fixing layer is placed on a support separate from the light-sensitive material, it is particularly preferable to contain a base and a base precursor. It's the execution gangway.

When the dye mordant is a polymer mordant, it also functions as a binder, so in such a case, it is not necessary to reduce the number of barrings or to use no binder. Conversely, if the binder also functions as a mordant, the dye mordant may not be used.

As the binder, the same ξ7 types as those used for photosensitive materials can be used.

The mordant used in the dye fixing layer of the present invention can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, the polymer mordant refers to a polymer 1. containing secondary and tertiary amino groups. Polymers having nitrogen-containing heterocyclic moieties and poly-7- etc. containing these 4u cation groups 1. The amount of men is 5.
0 yJ O~200°000, special Lo, 000
It is worth 50,000. For example, U.S. Patent No. 2
．． 54'8, 564, same? ;2+ /')84,4
No. 30, No. 3+! No. 481061, No. 3, 7
56. Vinyl pyridine polymers and vinyl pyridine L cationic polymers disclosed in US Pat.
9.096, British Patent No. 4,428.538, British Patent No. 1゜27'; No. 2,721,852
No. 2.798,063, Japanese Unexamined Patent Publication No. 1152-1983
No. 28, No. 54-145529, No. 54-12602
Aqueous sol type mordant disclosed in US Pat. No. 7, etc.; water-insoluble mordant disclosed in US Pat. No. 3,898,088; US Pat. No. 137333) A reactive mordant capable of forming a covalent bond with the dye disclosed in Mei MR Zen et al.; U.S. Pat.
Same No. 3,642,482, Same No.: N, 1188.7
() No. 6, No. 3, 557. No. 066, No. 3,
27+, z7-1i! , No. 3,271,148, JP-A-50-71332, b 3-3 G 328, 1-yari 52-155528, JP-A No. 53-125, JP-A-5
No. 3-1.024, as well as U.S. Pat. No. 2,675,316, U.S. Pat.
Mention may also be made of the mordants described in No. 156.

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 polymer mordants are shown below.

(1) Groups that have a 4L ammonium group and can be covalently bonded to gelatin (for example, aldehyde groups, chloroalkanoyl groups, chloroalkyl groups, vinylsulfonyl groups,
Hiricinium propionyl group, H = /l/ -13/
For example, a polymer having (-CH2-CH÷--→CH2-CHS101C-OC-O1 (2) F) Reaction products of copolymers consisting of repeating units of monomers and repeating units of other ethylenically unsaturated monomers and crosslinking agents (e.g. hisalkanesulfonates, bis-alkanesulfon-1.).

aryl group, or b At least R3-R5 one united peter It may form a ring.

X: anion (the above alkyl groups and aryl groups include substituted ones) (3) Polymer X represented by the following general formula: about θ+2J
~about j mol% y: about θ~about 0 mol% 2: about 10 to about phthalamic coefficient A: Monomer having at least two ethylenically unsaturated bonds B: Copolymerizable ethylenically unsaturated monomer Q: N , P bb Ro, R2, R3: an alkyl group, a cyclic hydrocarbon group, or at least two of ptb 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 halogen atom (alkyl group may be substituted) ) (b) Acrylic ester (C) Acrylonitrile (5) Repeating unit represented by the following general formula //
Water-insoluble polymer b having 3 or more R1, R2, R3: Each represents an alkyl group, and the total number of carbon atoms of R□ to R3 is 12 or more. (The alkyl group may be substituted.) X: Anion Various known gelatins can be used as the gelatin used in the mordant layer. For example, gelatin with different manufacturing methods such as lime-treated gelatin and acid-treated gelatin, or
It is also possible to use gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. If more than one is necessary, it can be used after being desalted.

Mixing ratio of polymer mordant and gelatin of the present invention and
The amount of J-mer mordant to be applied can be easily determined by those skilled in the art depending on the amount of dye to be mordant, the type and composition of the polymer mordant, and the image forming process to be used. 20/Jo~ and O/λ0 (weight ratio), and the amount of mordant applied is preferably O0j~19/m2.

A typical dye-fixing 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.

When the dye fixing layer is located on the surface, a retainer may be further provided if necessary. As such a protective iR, those generally used as protective layers of photosensitive materials can be used as they are.
When the dye fixing layer is provided on the dye fixing material separately from the photosensitive material and the dye fixing material, it is preferable to impart hydrophilicity to the protective layer so as not to inhibit the movement of the hydrophilic dye.
.

In the photographic photosensitive material of the present invention, an inorganic or organic hardener may be added to the photographic emulsion layer and other layers. For example, salts (chromium alum, chromium acetate), aldehydes (formua 7νdehyde, glyoxal, glucuralde, etc.), N-methylo-21 compounds (dimethylol urea, methylol dimethylhycuntoin, etc.) ), dioxane f
iRj% (2,3-dihy)'roxydioxane, etc.),
Active vinyl compounds (1,3,5-triacryloyl-hexahydro-3-) +J azide;, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (
2,4-dichloro-6-hydroxy-5-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

Furthermore, as the heating means for moving the dye, various means similar to those used in heat development as described above may be employed.

In the present invention, as well as the heat-developable photosensitive layer, a dye fixing layer,
For the protective layer, intermediate layer, undercoat layer, bank layer, and other layers, respective coating solutions are prepared and applied using the dipping method, air knife method, curtain coating method, or U.S. Pat. No. 3,681,294.
A photosensitive material can be prepared by sequentially coating a support onto a support and drying it using various coating methods such as the hopper coating method described in the book.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,76L,791 and British Patent No. 837,095.

In the present invention, various exposure means may be used.
I can do that. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used in normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, light emitting diodes, etc. can be used as light sources.

The original drawing may not only be a line image such as a technical drawing, but also a copy RnR with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original drawing may be carried out by contact printing over the original drawing, 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 a CRT or FOT,
It is also possible to form this image on a heat-developable photosensitive material either in close contact with it or through a lens, and then print it.

Furthermore, LEDs (light emitting diodes), which have recently seen significant progress, are being used as exposure means or display means in various devices. It is difficult to make an LED that effectively emits blue light, so in order to reproduce color images using LEDs, three types of LEDs that emit green, red, and infrared light are used. The portions of the photosensitive material that are sensitive to these lights may be designed to emit yellow, magenta, and cyan dyes, respectively.

That is, the edge sensitive part (edge) contains a yellow dye-donating substance, the red sensitive part (if) contains a magenta dye-donating substance,
It is sufficient that the infrared-sensitive portion (layer) contains a cyan dye-donating substance.Other combinations are also possible as required.

In addition to the method described above, in which the original drawing is directly attached or projected, the original drawing illuminated by a light source is read by a light receiving element such as a phototube or CCD, and this information is stored in the memory of a computer or the like and processed as necessary. After performing so-called image processing, this image information is reproduced on a CRT and used as an image-like light source, or there is a method of directly causing three types of LEDs to emit light based on the processed information for exposure. .

The image forming method of the present invention is an extremely simple image forming method that can perform completely dry processing in all steps from exposure to heat development and dye fixation without supplying any solvent from the outside. be. Furthermore, it is not only possible to maintain the sensitivity of conventional so-called silver halide photographic light-sensitive materials;
Since the formed dye image is fixed on a dye fixing material, the quality and storage stability of the dye image are extremely good, and the color reproducibility is good, and even though it is a completely dry process, color image reproduction is sufficient. This is extremely useful.

The image forming method of the present invention having such characteristics can meet not only the field of photography but also the recent demand for converting so-called soft images into hard images. Since the image is fixed in the dye fixing layer,
Since the image has good storage stability, it can be used for WJ delivery even when long-term storage is required, which is an improvement over conventional photographic technology, and the present invention has great significance.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Bottom margin (emulsion preparation example-1) Preparation of silver iodobromide emulsion 40 g of gelatin and 26 g of KBr were dissolved in 3000 ml of water. After stirring this solution while keeping it at 50°C, 34 g of silver nitrate was dissolved in 20 Qmj! of water. was added to the above solution over a period of 10 minutes.

Next, a solution prepared by dissolving 3.3 g of potassium iodide in 100 ml of water was added over 2 minutes.

The pH of the silver iodobromide emulsion thus prepared was adjusted, the emulsion was allowed to settle, and excess salt was removed.The pH was then adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g.

(Emulsion Preparation Example-2) 28 g of gelatin manufactured by No. 11 and 13.2 g of benzotriazole in silver emulsion of benzotriazole were added to 3 parts of water.
000m7! After stirring this solution while keeping it at 40°C, add 17g of silver nitrate to this solution and add 100m7 of water.
! was added over 2 minutes.

After adjusting the pH of this benzotriazole silver emulsion, allowing it to settle and removing excess salt, p+-t was adjusted to 6.0, yielding 1400 g of a hensitriazole silver emulsion.

(Emulsion Preparation Example-3) Preparation of benzotriazole silver emulsion containing photosensitive silver bromide 6.5 g of benzotriazole and log gelatin were added in 10 g of water.
100O! After stirring the solution while maintaining it at 50'C, a solution prepared by dissolving 8.5 g of silver nitrate in 100 mI of water was added over 2 minutes.

Next, a solution of 1.2 g of potassium bromide dissolved in 50 ml of water was added over 2 minutes, and the gJl emulsion was precipitated by pn adjustment. After removing excess salt, the pH of the emulsion was adjusted to 6.
Adjusted to 0. Yield was 200g.

(Example of preparation of dye fixing material) Preparation of dye fixing material R-1 Poly (methyl acrylate-N,N,N-)dimethyl-N-vinylbenzylammonium chloride) (
The ratio of methyl acrylate and vinylbenzylammonium chloride is 11) Dissolve LOg in water at 200 mA,
It was uniformly mixed with 100 g of 10% lime-treated gelatin. Spread this mixture onto a polyethylene terephthalate film for 2 minutes.
It was applied uniformly to a wet film thickness of 0 μm.

On top of this film, the following (a) to <e> were further mixed and dissolved, and then coated uniformly to a wet film thickness of 60 μm and dried to form a dye transfer aid layer.

(a) Urea 4g (b) Water
8mβ (C) 1 of polyvinyl alcohol (98% to saponified 1)
0% by weight aqueous solution 12g (d> 5% aqueous solution of the following compound 2ml ll(e)
5% aqueous solution of sodium dodecylbenzenesulfonate
0.5rnff (Photosensitive material preparation example-I
) Preparation of photosensitive material E-1 Preparation of dispersion of reducible dye-releasing agent Reducible dye-releasing agent IA-(9) 5g, electron donating substance ED-(22) 4g, 2-ethyl succinate- To 065 g of sodium hexyl ester sulfonate, 10 g of tritalesyl phosphate-1-('rCP), cyclohexanone 2Q rn I! was added and heated to about 60°C to dissolve. After stirring and mixing this solution and 100 g of a 10% solution of gelatin, the mixture was mixed with a homogenizer for 10 minutes. OOOR
Dispersed with PM. This dispersion is referred to as a reducible dye-releasing agent dispersion DP-1.

Next, a method for producing a photosensitive coating will be described.

(a) Photosensitive silver iodobromide emulsion (emulsion preparation example-1) 5B (b) Dispersion of reducible dye releasing agent D I) -133g <C> 10% ethanol solution of guanidine trichloroacetic acid 15ml (d ) 2.5% aqueous solution of the following compound QmI! (e) N,N-dimethylsulfonamide 10% aqueous solution
2 ml of water was added to (a) to (e) of 4 mβ or more, mixed, heated and dissolved, and then coated on a polyethylene terephthalate film to a wet film thickness of 60 μm and dried.

Furthermore, the following composition was applied as a protective layer on this film.

([) Gelatin 10% aqueous solution 35g (g) Guanidine trichloroacetic acid 10% ethanol solution
6mβ (h) 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate 4m7! (i) Water
A mixed solution of 55 ml was applied so as to have a film thickness of 25 μm, and then dried to produce a photosensitive material E-1.

(Example 1) The photosensitive material E-1 prepared in Photosensitive Material Preparation Example = 1 was imagewise exposed for 2000 luxte IO seconds using a tungsten light bulb, and then exposed to light for 30 minutes on a heat block heated to 130°C.
Heat evenly for seconds.

Next, the film surfaces of this photosensitive material and the dye fixing material R-1 produced in Production Example-1 were overlapped and brought into close contact, and heated uniformly for 30 seconds on a heat processor heated to 120°C.
When the dye-fixing material was peeled off from the light-sensitive material, a positive macenta color image was obtained on the dye-fixing material. The density of this positive image was measured using a Maches transmission density needle (D-504), and the maximum density for green light was 1.55.
The minimum value was 0°37. In addition, the gradation of the sensitometric curve is such that in the straight line part, the density difference is 1°0 for a 10 times the exposure amount difference.
It was 6.

From the above results, it was demonstrated that by using a dye fixing material containing a hydrophilic thermal solvent, a positive dye image with a large density difference between the maximum and minimum density can be obtained without supplying anything. .

(Example 2) Reducible dye-releasing agent IA- used in Photosensitive Material Preparation Example-1
Reducible dye releasing agent 113-(7) instead of (9)
Photosensitive materials F and -2 were prepared in exactly the same manner as in Photosensitive material preparation example-1, except that 5 g was used.

Next, each dye fixing material R- 2
~R-6 was produced.

Except that the photosensitive material E-2 used in Example 1 was used instead of the photosensitive material E-1, and the dye fixing materials R-2 to R-6 were used in place of the dye fixing material R-1, respectively. Example-1
Exposure, heating, and density measurement of the positive color image were carried out in exactly the same manner as described above. The results are shown in Table-1.

Table-1 Dye fixation Dye transfer aid Maximum Minimum fixed material
Concentration Concentration R-2N-methylurea (4g) L, 50 0.35R-3Pyridine-N-oxide (4g) 1.44 0.32R-4
Sulfonamide (4g) L, 61 0.39R-5 urea/
N-methylurea <2 g/2 g) 1.5B 0.3
4R-6 urea/N-methylurea/ethyleneurea/ethylurea 1.60 0.40 (l g/
I g/l g/l g) From the above results, by using a dye fixing material containing a hydrophilic thermal solvent, a positive dye image with a large difference in maximum and minimum density can be created without supplying anything. In addition, when dye fixing materials (R-5, 6) combined with a hydrophilic thermal solvent of 2 fffi or more are used, particularly sharp images with excellent surface gloss can be obtained. I was able to get it.

(Example 3) Instead of 25 g of silver iodobromide emulsion used in Photosensitive Material Preparation Example 1, 20 g of silver iodobromide emulsion and silver hensitriazole (
Emulsion Preparation Example-2) Using 1Og and using reducible dye-releasing agent IA-(9), use reducible dye-releasing agent 1 [1-(20) quinone form, reducible dye-releasing agent IA-(9)] Agent I
A-(7), or reducible dye-releasing agent III-(1B
Example of photosensitive material production except that 5 g of each quinone of ) was used.
In exactly the same manner as in 1, photosensitive materials E-3 to B-5 were prepared, respectively.
was created.

Exposure, heating, and density measurement of a positive color image were carried out in exactly the same manner as in Example-1, except that photosensitive materials E-3 to E-5 were used instead of photosensitive material E-1 used in Example-1. went. The results are shown in Table-2.

Table-2 Photosensitivity Dye donating property Hue Maximum Minimum material
Substance Concentration Concentration E-31-(20
) Quinone yellow 1. ．． 23 0.28E-4
1A-(7) Magenta 1.47 0.30E-5I
II-(1B) Quinone Cyan 1.58 0.32 From the above results, even when using the reducible dye releasing agent in Table 2, by using a dye fixing material containing a hydrophilic thermal solvent, It has been demonstrated that positive cyan, magenta, and yellow dye images can be obtained without any water supply.

(Example-4) The photosensitive material was prepared except that 25 g of benzotriazole silver containing silver bromide (Emulsion 11 Preparation Example-3) was used instead of 25 g of the silver iodobromide emulsion used in Photosensitive Material Preparation Example-1. Photosensitive material E-6 was produced in exactly the same manner as in Example-1.

Exposure, heating, and density measurement were carried out in exactly the same manner as in Example-1, except that photosensitive material E-6 was used instead of photosensitive material E-1 used in Example-1.

The maximum density of the positive magenta color image on the dye-fixing material was 1.6B, and the minimum density was 0.35.

(Example-5) l-Phenyl-4-methyl-4-oxymethyl-3 was added as an electron transfer agent to the coating solution of the photosensitive material of Photosensitive Material Preparation Example-1.
-Other than adding 0.4 g of pyrazolidone, operations and treatments were performed in exactly the same manner as in Example-1. The result j
The density of the q'd magenta color image is maximum 1.60 and minimum 0.
．． 29, and it was demonstrated that the addition of an electron transfer agent contributed to improving image quality.

(Example-6) The amount of guanidine trichloroacetic acid used in Photosensitive Material Preparation Example-1 was halved, and the reducible dye-releasing agent m-(17) was used instead of the reducible dye-releasing agent IA-(9). ) quinone form 5
Furthermore, instead of the electron-donating substance ED-(22), 4 g of the electron-donating substance ED-(1), ED-(13)
Photosensitive materials E-7 to E-7 were prepared in exactly the same manner as in Photosensitive material production example-1 except that 4g or ED-(23) was used.
E-9 was produced.

Further, dye-fixing material R-7 was prepared in the same manner as in dye-fixing material preparation example-1 except that 0.4 g of guanidine trichloroacetic acid was added to the coating solution used in dye-fixing material preparation example-1.

The above photosensitive materials E-7 to E-9 were imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb, and then brought into close contact with the dye-fixing material R-7 with their film surfaces facing each other.
Heated on a heat block at 130°C for 45 seconds.

When the dye-fixing material was peeled off from the light-sensitive material, a positive color image was obtained on the dye-fixing material. The density of these positive color images was measured using a Macbeth density needle (D-504). The results are shown in Table-4.

Table-4 Photosensitive material Electron donating substance Maximum concentration Minimum concentration E-4
ED-(22) 1.22 0.28E-5ED-
(13) 1.39 0.31B-6ED-(23
) 1.51 0.25 The above results demonstrate that even when heat development and dye transfer are performed simultaneously, a positive dye image having a high maximum density and a low minimum density can be obtained.

Patent Applicant Fuji Photo Film Co., Ltd. Agent Patent Attorney Taki 1) Kiyoshi Procedural Amendment April 18, 1980 Director General of the Pedera Agency Kazuo Wakasugi 1, Indication of Case 1980 Patent VA No. 048750 2 , Name of the invention Dry image forming method 3, Relationship with the person making the amendment Patent applicant Minamia Shigara Nakanuma Address 210 Nakanuma, Minamiashigara City, Kanagawa Name Name (520) Fuji FFJ Shin Film Co., Ltd. Minoru Onishi Representative Minoru Ohnishi 4 , Agent ■ 166 Address 4-29-11-6 Koenji Kita, Suginami-ku, Tokyo
, Subject of amendment Column 7 of "Detailed Description of the Invention" of the specification, Contents of amendment ■) i? of the invention? - Detailed Description, page 8, line 16, 1 - Of the images and mobile dye images,” is replaced by [i! ! !
i-image and the mobile dye image obtained in the exposed area.

243

Claims (1)

[Claims] A positive silver halide photosensitive material having at least a photosensitive silver halide binder, an electron donor and/or an electron transfer agent, and a reducible dye releasing agent is placed on the support after or simultaneously with the image exposure. By heating, the mobile dye formed in the unexposed area is moved under high temperature conditions in the presence of at least one hydrophilic thermal solvent,
A dry image forming method characterized by fixing the dye on a dye fixing layer.