JPH0365535B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses a positive silver halide photosensitive material.
The present invention relates to a completely dry image forming method. More details
In the present invention, the unexposed area is obtained by heat development treatment.
dyes, especially without using systems containing solvents.
Then fix it on the dye fixing layer by heating.
Regarding the method. Photography using silver halide is different from other photographic methods,
For example, compared to electrophotography and diazophotography, the sensitivity is
Because it has excellent photographic characteristics such as gradation adjustment and gradation adjustment,
It has traditionally been the most widely used. In recent years, halo
Image forming processing method for photosensitive materials using silver germide
From conventional wet processing using developer, etc., to heating, etc.
By switching to dry processing, images can be easily and quickly obtained.
Techniques have been developed that allow images to be obtained. Heat-developable photosensitive materials are known in the art.
Regarding heat-developable photosensitive materials and their processes,
“For example, the basics of photographic engineering (published by Corona Publishing, 1979)
pages 553-555, video information published in April 1978, page 40,
Nebletts Handbook of Photography and
Reprography 7th Ed. (Van Nostrand Reinhold
Company) pages 32-33,
U.S. Patent Nos. 3152904, 3301678, 3392020
No. 3457075, British Patent No. 1131108, No.
No. 1167777 and Research Disclosure
Magazine, June 1978 issue, pages 9-15 (RD-17029)
It is listed. Much has already been written about how to obtain color images by dry methods.
method has been proposed. Oxidized form of developer and cap
Regarding the method of forming color images by combining with color
In US Pat. No. 3,531,286, p-phenylene
Diamine reducing agent and phenolic or active methylene
In U.S. Pat. No. 3,761,270, the p-coupler is
Aminophenol reducing agent received Belgian patent no.
Issue 802519 and Research Disclosure Magazine
In the September 1975 issue, pages 31-32, sulfonamide
Nor-based reducing agents are also used in U.S. Pat. No. 4,021,240.
Sulfonamide phenolic reducing agent and 4 equivalent cap
A combination with RA has been proposed. However, in this method, after heat development
A layer of reduced silver and a color image occur simultaneously in the exposed area
Therefore, there was a drawback that the color image became muddy. This lack
As a way to solve this problem, silver images are treated with liquid.
Either remove it or remove only the dye from other layers, such as the image-receiving layer.
There is a method of transferring onto a sheet containing
It is impossible to distinguish between the color and the color and transfer only the color.
It has the disadvantage that it is not easy to use. In addition, a nitrogen-containing heterocyclic group is introduced into the dye to form a silver salt.
The method of releasing the dye by heat development is
Research Disclosure Magazine May 1978 Issue 54
Pages 58 to 58 (RD-16966). child
In this method, the dye is removed in areas not exposed to light.
Because it is difficult to suppress release, clear
I can't get an image and it's not a common method.
stomach. Also, a positive color image is formed using a heat-sensitive silver dye bleaching method.
For information on how to
Closure Magazine April 1976 issue, pages 30-32 (RD-
14433), December 1976 issue of the same magazine, pages 14-15 (RD-
15227), U.S. Patent No. 4,235,957, etc.
Bleaching methods are described. However, in this method, bleaching of the dye
Stack and heat activator sheets to speed up the process.
Extra steps and materials are required, and the obtained
Gradual reductive bleaching due to free silver etc. where color image coexists
It is said that it cannot withstand long-term storage due to
It had drawbacks. Also, a method of forming color images using leuco dyes.
For example, U.S. Pat. No. 3,985,565;
Described in No. 4022617. But this method
The next step is to stably incorporate leuco dyes into photographic materials.
It is difficult to use, and it has the disadvantage of gradually discoloring during storage.
had. The present inventors have already solved the drawbacks of these conventional methods.
We provide friendly photosensitive materials that can
For this purpose, we provided an image forming method (patent application 1983).
−157798). This is essentially a water-free condition.
The simple method of heating with
A photosensitive material capable of releasing an aqueous dye and its mobility
Dye is added to the dye fixed layer mainly in the presence of a solvent.
Regarding an image forming method characterized by moving
It was something to do. The present inventors further discuss the earlier invention.
As a result of recommending research, in a virtually water-free state.
Mobile hydrophilic material formed by heating
heating the sex dye without supplying any solvent
By doing so, it can be easily moved.
They discovered this and arrived at the present invention. Therefore, the first object of the present invention is to
produced by heat development treatment performed at the same time as exposure.
Supplying hydrophilic dyes, especially external solvents
To provide a method of fixing the dye to a dye fixing layer without
It is in. A second object of the present invention is to
Multiple parents created by heat development
Aqueous dyes, especially without external solvent supply.
In order to provide a method for fixing the dye to the dye fixing layer,
be. That is, the present invention provides at least a photosensitive layer on a support.
silver halogenide, binder, electron donor and/or
Contains an electron transfer agent and a reducible dye releasing agent
A positive silver halide photosensitive material is exposed after image exposure or
Unexposed by heat development treatment at the same time as exposure
The hydrophilic dye produced in the
In the presence of a hydrophilic thermal solvent, the
The dye is transferred to the dye fixing layer under warm conditions to create a positive color.
Dry image formation characterized by forming a raw image
It's a method. In the photosensitive material according to the present invention, after image exposure
or substantially water-free, simultaneously with image exposure
Due to heating in the state, in addition to the silver image, at the same time,
Compatible with undeveloped silver halide in unexposed areas
As a result, a hydrophilic mobile dye is obtained. The present invention
This heat development process is called "heat development process".
However, in this case, it is obtained in the unexposed area.
Since the pigment used in the dye is a hydrophilic mobile pigment, it is hydrophilic.
In an atmosphere where the sex pigment has an affinity, this
can be transferred to the dye fixing layer, and this
Therefore, dye images with excellent image quality and storage stability can be obtained.
You can get it. This step in the present invention
This is a "dye fixation" process. In this case hydrophilic dye
An atmosphere that has an affinity for mainly supplies the solvent.
What can be achieved by doing
Although it has already been disclosed (Japanese Patent Application No. 56-157798),
In the present invention, a hydrophilic thermal solvent is present.
By creating an atmosphere that has affinity with hydrophilic dyes,
In order to realize Qi, it is necessary to supply a solvent especially
Therefore, there is no process from exposure to heat development and dye fixation.
No solvent is supplied externally during the entire process.
Completely dry process with no need for color and image
It is possible to form dye images with good image reproducibility.
Ru. This principle is based on the autopositive emulsion of light-sensitive materials.
Even when using an emulsion, when using a negative emulsion
However, there is nothing essentially changed, so
When using a dimulsion, the silver obtained in the unexposed area
Among the images and the mobile dye image obtained in the exposed area,
Except that only the dye image is transferred to the dye fixing layer.
color and color in the same way as when using a negative emulsion.
It is possible to obtain dye images with good image reproducibility.
Ru. The heat development treatment in the present invention substantially removes water.
This is done by heating in a state that does not contain
However, here, heating means heating between 80℃ and 250℃.
Flavored and substantially water-free means no reaction.
The system is in equilibrium with the moisture in the air, causing a reaction.
specifically supplying water to stimulate or accelerate the reaction.
It means never. This kind of condition
is “The theory of the photographic
process”4th Ed. (Edited by T.H.James,
Macmillan) on page 374. In the present invention, as a reducible dye releasing agent,
By selecting various compounds, released
Since you can choose the pigment, you can reproduce various colors.
can be done. Therefore, in choosing that combination
Therefore, it is possible to make the color more colorful.
In addition to monochromatic pigment images, multicolor images can be used in
Monochromatic images include monochromatic images that are a mixture of two or more colors.
is also included. In the method of forming a dye image of the present invention, the dye image is originally hydrophilic.
Does not release dye but becomes hydrophilic by being reduced
Diffusion-resistant dye-donating substances that release color pigments (this
In the specification, this is referred to as a reducible dye releasing agent.
image exposure and heat development.
The exposed photosensitive silver halide is
Photosensitive silver halide and reducing electron transfer as catalysts.
Redox reaction between the delivery agent and/or electron donor
occurs, a silver image is generated in the exposed area, and the electron transfer agent and
and/or the electron donor is oxidized. On the other hand, unexposed
In the section, a dye releasing agent that can be reduced by heating is used.
However, the electron transfer remaining as an inverse function of the silver image
Reduction occurs as a result of reaction with agents and/or electron donors.
and becomes a reduced form, thus leaving a hydrophilic substance in the unexposed area.
A mobile dye is released. The compound called reducible dye releasing agent used in the present invention
A first example of a compound that undergoes intramolecular nucleophilic substitution is
Ballast stabilized to release mobile pigments
Examples include compounds. The ballast stabilizing compound is
Before nucleophilic substitution can occur, at least one
Contains precursors of nucleophilic groups that need to accept electrons.
I'm reading. The reducible dye releasing agent used in the present invention is an electron
donor (i.e. reducing agent and reducible dye releasing agent)
is reduced to a form that undergoes intramolecular nucleophilic substitution.
provide the necessary electrons to make it possible to
It is a compound that becomes useful when combined with
be. The electron donor is photographed in an image-like dispersed state by exposure to light.
When the given state is reached in the true element, the electron
Ballast-stabilized electron-accepting nucleophile from donor
Electrons are donated to substituted compounds according to the image pattern.
As a result, image-wise replacement occurs and the color changes.
element is released. Particularly useful in heat-developable color photographic processes and photographic elements.
The reducible colors of the present invention have been found to be useful for
The first compound of the elementary release agent is expressed by the following model formula:
It can be expressed as (Ballast stabilized carrier) x - (Demand
electronic leaving group) y-(mobile dye component) z However, x, y and z are positive integers, preferably
1 or 2; this is bound to one ballast group
Compounds with one or more mobile components
or one or more attached to one mobile component.
Includes compounds with ballast;
The stabilized carrier is transferred under thermal diffusion transfer conditions.
A group capable of rendering the compound immobile.
; said ballast stabilized carrier has a
A nucleophilic group when it accepts at least one electron
(Causes intramolecular nucleophilic substitution with the electrophilic cleavage group)
This includes groups that provide a group that can be used. The reducible dye releasing agent is ballast stabilized.
the carrier is coupled to each mobile component.
Each bonding group contains an electrophilic leaving group.
The nucleophilic group generated by reduction is an electrophilic dissociative group.
Some groups become ballast stable as a result of reacting with leaving groups.
remains with the converted carrier, and some groups remain movable.
It remains with the sexual components. In general, intramolecular nucleophilic substitution compounds are
In a dimensional structure, they coexist closely and their
Nucleophilicity that can cause intramolecular substitution reactions due to
It is a compound having an electrophilic group and an electrophilic group, and the present invention
Intramolecular nucleophilic substitution occurs when the nucleophilic precursor
What happens after accepting at least one electron
It is. In this case, electrophilicity and nucleophilicity are respectively
These groups are held in positions where they can react.
Any compound (polymeric compound, macroscopic compound)
Click compound, polycyclic compound or enzyme-like structure
etc.). but
However, nucleophilic groups and electrophilic groups are organic rings or
such as those that easily form organic rings through intramolecular reactions.
It is preferable to occupy any position in the organic compound.
Preferably, the nucleophilic group and the electrophilic group are 3-
or a 5- to 7-membered ring, more preferably a 5- or
This is the position where a 6-membered ring can be formed (4
-Membered rings are generally difficult to form in organic reactions.
Are known). In this way, the intramolecular nucleophilic substitution according to the present invention
Although the compound is relatively reactive, it is hydrophilic.
The initial release of the dye compound is due to the reduction of the nucleophilic precursor group.
processing conditions, unless they occur as a direct function of the original.
It needs to be stable under certain conditions. The reducible dye-releasing agent used in the present invention is
Nucleophilic precursor groups bonded through groups and electrophilic
cleavage group.
This linking group may be an acyclic group, but may be a cyclic group.
It is preferable that it is a group of some very desirable ingredients
In the example, the nucleophilic precursor group and the electrophilic group
are both bonded to the same aromatic ring structure, but
In this case, the ring structure is a heterocyclic structure even if it is a carbocyclic structure.
It may be a ring structure, and each group may be a separate ring structure.
Also includes fused rings, such as those that can be present on
be done. In particular, both groups are directly attached to the same aromatic ring.
In this case, the aromatic
It is particularly preferred that the aromatic ring has a carbocyclic structure. Preferred specific examples of the reducible dye releasing agent of the present invention
The first is the reaction center of the nucleophilic reaction and the reaction center of the electrophilic reaction.
Between each atom serving as a reaction center, 1 to about 5
atoms, preferably 3 or 4 atoms
and can be expressed by the following general formula. General formula () In the formula, w, x, y, z, n and m are positive integers 1 or
is 2; ENuP is an electron-accepting nucleophilic group precursor
For example, precursors of hydroxyamino groups [nito]
Roso group (NO), stable nitroxyl free radical
Cal (N-O.), and preferably a nitro group
(NO₂] or a precursor of a hydroxy group [preferably
Preferably, it is an oxo group (=O)], or
imine group (which accepts electrons in an alkaline environment)
hydrolyzed to oxo group before
Well, R¹is less than 50 atoms, preferably less than 15
An organic group containing an atom, preferably a cyclic organic group
(including ring groups with a ridge), or polycyclic groups
(5 to 7 atoms in the ring to which ENuP and E are bonded)
), and more preferably
or an aromatic ring having 5 to 6 members in the ring,
or a carbocyclic group, such as a benzonoid group,
or a heterocycle containing a non-aromatic ring (ENuP is part of the ring)
It is. That is, ENuP has a nitrogen atom in the ring.
is a nitroxyl group). ;R²and R³is 2
Divalent organic group containing 1 to 3 atoms in the valent bonding group
and may be an alkylene group, oxa
alkylene, thiaalkylene, azaalkylene,
May be an alkyl- or aryl-substituted nitrogen
stomach. This includes large groups in the side chains on the linking group.
and can function as a ballast.
a group containing at least 8 carbon atoms;
The group of¹X when itself is a ballast group¹in
be. As a specific example of this, for example, R³but
Dialkyl-substituted methylene bond, e.g. Q is an oxygen atom
Child and R¹and ENuP forms a quinone
Dimethylalkylene is useful for
and Q provide electrophilic cleavable groups, where E
is the center of the electrophilic reaction, preferably the thiocarbon
A carbonyl group containing a carbonyl (-CS-) group, or
It is a sulfonyl group. ;Q is E and X²monogen between
A group that provides a child bond, where a monoatom is
Periodic table a or in valence state of -2 or -3
is a group A nonmetal atom, such as an oxygen atom or a sulfur atom.
a selenium atom, preferably an amino group
It is a nitrogen atom that provides These atoms are X²of
provides two covalent bonds linking E, but the
As a result, X²When forming a 5- to 7-membered ring with
If those atoms are trivalent atoms,
is a hydrogen atom, 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms
Alkyl group containing 10 carbon atoms (substituted carbon
atoms and carbocyclic groups), or 6 to 20 carbon atoms
Aryl groups containing children (including substituted aryl groups)
can be mono-substituted by this
Examples include, for example, pyridine or piperidine.
Examples include N groups. ;X¹is R¹,R²or
R³a substituent on at least one of
X¹Or Q-X²One of the layers is in the photo element layer.
a buffer large enough to render the compound immobile at
one represents a last group, the other a photographically useful color
element or its precursor. X¹and Q-X²Is that so?
E or R for each part¹necessary to connect to
Also includes linking groups. ;R¹,R²and R³is the part of Q from E
To allow intramolecular nucleophilic release, ENuP
selected to provide substantial proximity to E.
It will be done. These are reaction centers for nucleophilic reactions.
The atom that is the reaction center of the electrophilic reaction and the atom that is the reaction center of the electrophilic reaction.
to provide 1 or 3 to 5 atoms between the child and
selected, thereby making the compound 3- or 5-
7-membered ring, preferably 5- or 6-membered ring
, a group Q-X from the electrophilic group²Intramolecular equation of
all that can be formed upon nuclear substitution.
Ru. For example, E is a carbonyl group and Q is an amino
groups, preferably alkyl- or aryl-substituted amino
When it is a group of²is Q via the sulfonyl group
is connected to Q−X²The release of sulfo
A nyl group is provided. In the compound of general formula () above, electrophilic
The stability and release rate of the child-cleavable group are determined by -(E-
Q) - a certain atom in the bonding group adjacent to the group
or can be changed by using groups.
Wear. E is a carbonyl group and ENuP is an oxo
group, or in certain other cases, all of E.
R next door³It is desirable to have an amino group therein.
In some embodiments, immediately adjacent to Q in the linking group,
It is also desirable to have a specific group, in which case
is (Q−X²) is (Q-R⁹−X³) on the basis of
Ru. R here⁹is the fragrance defined later in this specification.
It is a group like an aromatic group. of the ballast group in the compound of general formula () above.
The properties are mainly due to the compound part on the ballast side of E.
As long as it brings about the function of immobility,
Not subject to any restrictions. Besides the molecules on the remaining side of E
The part generally makes it mobile after release, and
Sufficient flexibility to make it mobile in alkaline media.
Contains a solubilizing group. Therefore, if R¹,R²as well as
The remainder of R3 is added to the compound to make it immobile.
X if it provides sufficient insolubility for¹is ratio
It may be a relatively small group. however,
X¹or (Q−X²) functions as a ballast.
where they are generally straight-chain alkyl groups, as well as
Consisting of aromatic groups of the benzene and naphthalene series
ing. Typical useful ballast functional groups include at least
8 or more carbon atoms, preferably at least 14
Contains carbon atoms. X¹is the ballast
If so, it is R¹,R²or R³desired replaced with
It can be one or more groups that confer immobility.
Thus, for example, two small groups, e.g. 5 to 12
Two groups containing carbon atoms, 8 to 20 carbon atoms
To obtain the same immobility as one long ballast group containing
It can be used for A large number of ballast groups are used.
If available, the main part of the ballast group and its
The bonded aromatic ring is formed through an electron-withdrawing group.
Sometimes it is convenient to combine. As used herein, the term "nucleophilic group" refers to covalent
an atom that has a pair of electrons that can form a bond
Or it means an atomic group. This type of base is often
For example, an ionizable group that reacts as an anionic group.
be. The term “electron-accepting nucleophilic precursor group” refers to
After accepting at least one electron and being reduced, the desired
Means a precursor group that provides a nuclear group. electric
A child-accepting nucleophilic precursor group is cyclic in nature.
less nucleophilic than the original group or a nucleophilic reaction
It has a structure that makes it difficult to access the reaction center. A nucleophilic group is a nucleophilic group such as the oxygen atom in a hydroxyl group.
It may also contain one functional group. nucleophile
A nucleophilic group is one in which either the nitrogen atom or the oxygen atom is nucleophilic.
Hydroxyl that can be the center of reaction
As in the case of amino, it acts as a reaction center for nucleophilic reactions.
can contain one or more atoms that can be present invention
reacts during the nucleophilic group on the intramolecular nucleophilic substitution compound of
If there is one or more atoms that can be the center, nucleophilic
Target attacks and substitutions generally form the most favorable ring structure.
to pass through the reaction intermediates that can be formed.
happen. ; That is, if the acid of the hydroxylamino group
Elementary atoms often form a 7-membered ring, and nitrogen atoms
It is assumed that the children often form 6-membered rings.
For example, the most active reaction center in a nucleophilic reaction is generally nitrogen.
It can be said that it is an elementary atom. As used herein, the term "electrophilic group" refers to
accepting a pair of electrons to form a bond
means an atom or atomic group capable of representative
The electrophilic group is sulfonyl (-SO₂−), Calbo
(-CO-) and thikiocarbonyl (-CS
−), and in this case, the carbonyl group
The sulfur atom of an elementary atom or a sulfonyl group is
Becomes a reaction center for electronic reactions and is partially positively charged
can grow. Next, the term "electrophilic cleavable group" is used herein as
(-E-Q-) is used herein to refer to the group (-E-Q-).
Here, E represents an electrophilic group, and Q represents E and X.²with
a leaving group that provides a monoatomic bond between
group), where the single atom is 2 or 3
It is a nonmetallic atom that has a valence. The leaving group
is released from an electrophilic group and accepts a pair of electrons.
can do. Nonmetallic atoms are trivalent atoms.
For example, hydrogen atoms, alkyl groups (substituted
(including substituted alkyl groups and dichloroalkyl groups), a
Ryl group (including substituted aryl group), or X²with
for example pyridine or piperazine groups.
Among the atomic groups necessary to form a 7-membered ring
Can be substituted with selected substituents. a certain state
, the methylene group, i.e. -CH₂- is the above general formula
Used as an electrophilic group when m is 2 in ()
I can be there. In this case R³is 2-substituted methylene
Alkylene groups containing
or diarylmethylene group, which is
R¹directly attached to the aromatic group provided by
There is. In this embodiment, X²is a leaving group.
a bonded carbonyl group, sulfonyl group, or
can contain phosphono groups and therefore
, carboxy group, sulfonate group or phosphonate group.
Nucleophilic groups and electrophilic groups capable of releasing ate groups
of the disubstituted methylene group in the bond between the cleavable group and the cleavable group.
The presence clearly orients the released group more favorably.
This causes the methylene group to become an electrophilic group.
Reaction rate of intramolecular nucleophilic substitution when used as
degree increases. The reducible dye releasing agent of the present invention is characterized by the reaction of the compound.
Substituents can be included that alter the rate. child
Substituents such as, for example, R¹expressed by
It is located on a cyclic aromatic group, but especially when ENuP is
When it is a tro group, ENuP and X¹has a join of 1
The aromatic ring has at least one, preferably two electrons
Contains an attracting group (electron with drawing group)
I'm reading. These electron-withdrawing groups are positive
those with Hammett sigma values, e.g. sulfonate
It is a nyl group. Electron-withdrawing substituent is R¹a place that is located above
In this case, the reducing compound of the present invention represented by the general formula ()
Original dye releasing agents generally undergo reduction more easily.
In order to
Can be used. However, according to the present invention,
For other reducible dye release agents, fast reduction
More powerful electron donors to achieve speed
It is necessary to use it. For example, if the nucleophilic precursor group
In one embodiment, which is a tro group, preferred
benzisoxazolone electron donor together with the desired
To achieve the rate of reduction, at least two
Electron-withdrawing groups are used on the aromatic ring. The term “immobile” is used herein.
is used in the sense normally used in photography. The word “immobile” is also used interchangeably.
Ru. The term “mobile” is used for the materials of this invention.
If there is, it means the opposite of the above. In certain embodiments, useful reducible dyes of the invention
The release compound is a ballast-stable compound with the following structure:
It is a chemical compound. Here ENuP is for the hydroxy nucleophilic group
Electron-accepting nucleophilic precursor (imino group and preferably
contains an oxo group); G¹is imino(al)
(including kylimino) group, sulfonimide group, R^Four
or R⁶Regarding the cyclic group or ENuP formed with
Any group selected from the groups specified in
Preferably G¹is the para of ENuP above in the formula
position; E is an electrophilic group and it
Bonyl-CO- or thiocarbonyl-CS- group,
It can be any group, preferably carbonyl.
Q is E and R⁹proposes a monatomic bond between
A monoatom here means a group that provides nitrogen, for example,
atoms, such as oxygen atoms, sulfur atoms, selenium atoms
-2 or -3 origin of genus a or a of the periodic table
It is a nonmetal atom in a valence state. In this case, the original
child is E to R⁹provides two covalent bonds to connect to
However, when Q is a trivalent atom, for example, hydrogen
atoms, alkyl groups (containing 1 to 10 carbon atoms)
(including substituted alkyl groups), aromatic groups (5
contains ~20 carbon atoms, an aryl group,
(including substituted aryl group) or R⁹with 5-7
Atom groups necessary to form a membered ring (e.g. pyridine
or piperidine group), etc.
may be substituted by; R⁷is the bonding group
Alkylene group containing 1 to 3 carbon atoms (without substituents)
containing an alkylene group), or in the bonding group
at least one methylene of
an arylmethylene linking group, and preferably
is an alkali containing one carbon atom in the divalent bonding group.
Kylene groups, such as methylene linking groups or dialkyl
- or diaryl-substituted methylene bonding group.
; n is an integer of 1 or 2; R⁹at least
aromatic group containing 5 atoms, preferably 5 to 20 atoms
can be a heterocyclic group, such as a pi
lysine, tetrazole, benzimidazole,
cores such as zotriazole or isoquinoline.
Also included are groups containing 6 to 20 carbon atoms.
a carbocyclic arylene group (preferably a phenylene group)
Phenylene substituted with lene group or naphthylene group
and naphthylene groups). Furthermore
R⁹is an alkylene group containing 1 to 12 carbon atoms (position
aliphatic hydrocarbons (including substituted alkylene groups)
It may be a group. ;R⁸contains 1 to 40 carbon atoms
Alkyl groups (substituted alkyl groups and cycloalkyl groups)
aryl containing 6 to 40 carbon atoms
group (including substituted aryl groups), or
Substituent X as defined¹It may be ;R⁶,R^Four
and R^Fiveeach represents a 1-atom substituent such as a hydrogen atom or
may be a halogen atom, but is preferably a halogen atom.
Atomic substituents e.g. alkyl containing 1 to 40 carbon atoms
(including substituted alkyl groups and cycloalkyl groups)
), alkoxy group, alkoxy group containing 6 to 40 carbon atoms
Ryl group (including substituted aryl group), carbonyl group
group, sulfamyl group, sulfonamide group.
or if they are in adjacent positions of the ring.
R⁶and R^Fiveis R^Fourand R^Fivetogether, the block
With the rest of the molecule containing the rigid ring,
When a 5- to 7-membered ring can be formed
are each a substituent X¹It may be. However, R⁹
is an aliphatic hydrocarbon group such as an alkylene group
If R⁶and R^Fouris not a polyatomic substituent
Naru, Mata R^Fiveis preferably a polyatomic substituent,
and G¹is defined for ENuP
In the case of an electron-accepting nucleophilic precursor group, G¹
R adjacent to^Fouror R⁶The substituent is the following group a large number of which can be released by nucleophilic substitution.
A compound having a group can be provided. X¹
is given in at least one substituted position,
X¹and -(Q-R⁹−X³) each of the above compounds
to make it immobile in the binder layer of the photographic element.
A ballast stabilizing group large enough for
group) or X¹and -(Q-R⁹−X³)
If one of them is a ballast group, the other
is a photographically useful group such as a photographic reagent, preferably
such as image dyes or image dye precursors.
This is a necessary group for dye-providing substances. R⁷teeth
Select one that makes it easier for the nucleophilic group to approach E.
and intramolecular nucleophilic reaction with release of Q from E
is allowed. Preferably, R⁷is the nucleophilic group
The atom that is the reaction center of the nucleophilic reaction and the electrophilic
3 between the atom that is the reaction center of the electrophilic reaction of the group
chosen to provide ~5 atoms, thereby
The compound has a 5- to 8-membered ring, more preferably
The 5- to 6-membered ring is replaced by -(Q
−R⁹−X³) due to intramolecular nucleophilic substitution of the group
can be achieved. Useful compounds of this type
Representative ones are the following compounds IA-1 to IA-9
etc. The compound of the above general formula is, for example, R⁸is balki
When the substituent is a substituent that causes steric hindrance.
has improved Dmin and increased stability after processing.
The overall imaging characteristics can be exhibited. this
Like R⁸A typical group that can be
lohexyl, isopropyl, isobutyl, and
There is Njiru. R^Four,R^Fiveand R⁶is a steric hindrance to the adjacent part of the quinone ring.
When containing bulky substituents that give
Also, improved image forming properties can be obtained. representative
Substituents include α- and β-substituted alkyl groups such as α-methyl
alkylcyclohexyl, isopropyl, α-
Methylbenzyl and pt-butyl-α-phene
Includes chill etc. This bulky substituent can be used in compounds with the above structure.
It seems more advantageous to have it inside,
They also occupy other similar positions in the compound.
can also be used to improve
Gives photographic properties. The compound represented by the general formula (IA) of the present invention is
For example, synthesis using the method of JP-A No. 53-110827.
I can do it. In certain preferred embodiments, the compounds of the invention
The compound is a compound having the following general formula (B).
Ru. General formula (B) Here, ENuP is the electron acceptor of the hydroxylamino group.
soluble precursors, e.g. nitroso (NO), stable nitrogen
troxyl group and preferably nitro group (NO₂)
A together with the rest of the general formula above is 5-
~Contains the atomic groups necessary to form a 6-membered aromatic ring.
This group also includes polycyclic aromatic ring structures. Here, an aromatic ring is a carbocyclic ring or a heterocyclic ring, such as a ring
It may be a group containing an aromatic onium group,
Preferably, A is a benzene ring or a naphthalene ring.
Represents a group necessary to form a carbon ring such as; W
is an electron-withdrawing property with a positive Hammett sigma value
cyano, nitro, fluoro, chloro
b, bromo, iodo, trifluoromethyl, tri
Alkylammonium, carbonyl, N-substituted carbon
rubamoyl, sulfoxide, sulfonyl, N-position
containing groups or esters such as substituted sulfamoyl etc.
Contains; R¹²contains hydrogen atoms, 1 to 30 carbon atoms
substituted or unsubstituted alkyl group, or 6 to 30 carbon atoms
Substituted or unsubstituted aryl group containing elementary atoms; R³
is a divalent organic group containing 1 to 3 atoms in the bonding group.
For example, alkylene group, oxaalkylene
group, thiaalkylene group, azaalkylene group, alkylene group,
Kyl or aryl substituted nitrogen, etc., preferably
Preferably, at least one dialkyl group is present in the bonding group.
Alkyl- or diaryl-substituted methylene
is a ren group; m and q are positive integers 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 substituted position on any part of the aromatic ring structure of A.
is a substituent; E and Q provide electrophilic cleavage groups
Here, E is the reaction center of the electrophilic reaction, and is a preferable
Preferably includes thiocarbonyl (-CS-)
carbonyl group or sulfonyl group
Ru. Q is E and X²provide a monatomic bond between
group, where Q is an oxygen atom, a sulfur atom,
is a nitrogen atom that provides an amino group, or a nitrogen atom that provides an amino group.
but preferably 1 to 20 atoms, more preferably 1 to 20 atoms
Amino with an alkyl substituent containing 10 atoms
group, substituted alkyl group or Q-X²with 5
~Atom groups necessary to form a 7-membered ring, e.g., pyri
zine group or piperidine group; n is an integer of 1 to 3.
a number, preferably 1;²is Q and
Both contain image dye-providing substances such as image dyes or image dyes.
is an image dye precursor;¹is as defined above
ballast-providing group, preferably 8 to 30
a substituted or unsubstituted alkyl group containing a carbon atom,
or 8 to 30 carbon atoms (required for bonding to the aromatic ring)
substituted or unsubstituted aryl containing (including bonding groups)
It is the basis. However, X present in the above compound¹or
R¹²at least one of the compounds of (B) above
is immobile and in the alkali-permeable layer of the photographic element.
It is a group large enough to be immobile. In other words, good
Preferably X¹or R¹²at least one of 12 to 30
Contains carbon atoms. A large number of groups are present in the compound shown by the above formula
In some cases, they may be the same or different.
It's good to wear. That is, p is 3 and each (R¹²−
W)- is selected from a variety of different substituents specified
can be Electron withdrawing mentioned for compounds of above formula
A functional group is a group that has a positive Hammett sigma value.
and preferably has a sigma value greater than 0.2.
as a substituent on an aromatic ring, or as a substituent on an aromatic ring.
It is a group that has a large combination of effects.
Hammett sigma value is Steric Effects in
Organic Chemistry. John Wiley and Sons,
Inc., 1956, p.570-574, and Progress in
Physical Organic Chemistry, Vol.2,
Interscience Publishers, 1964, pp. 333-339.
Calculated according to the method listed. Typically useful with positive Hammett sigma values
Electron-withdrawing groups include cyano, nitro, fluoro,
Bromo, iodo, trifluoromethyl, trial
Kylammonium, carbonyl, N-substituted carba
moyl, sulfoxide, sulfonyl, N-substituted sulphate
Includes rufuamoyl, ester, etc. “Electron absorption
The term "aromatic ring having an attractive substituent" is used herein to mean
When used, it is an onium compound in the ring
It also refers to a bond for other groups such as a ballast group.
Indicates a group that is directly substituted on a ring that can become a merging group.
vinegar. The electron-withdrawing group is present in the ring in the compound of the formula below.
contains similar groups; E, Q, X here¹and X²is as defined above
It is. Compound represented by general formula (B) of the present invention
can be synthesized by the method of JP-A-53-110827.
Wear. Next, specific examples of compounds represented by general formula (B)
shows. As a second example of the reducible dye releasing agent of the present invention
Compound represented by general formula (A) or (B)
There is. During the ceremony (Nuox)¹and (Nuox)²even if each of them is the same
may be different, such as O= group or HN= group
represents an oxidized nucleophilic group, Z is R¹⁴and R¹⁵
is electronegative to the carbon atom that carries the
represents a divalent group (e.g. sulfonyl group), Y is Z
Represents a group that becomes a mobile dye after being released with the group.
vinegar. R¹¹,R¹²and R¹³each is a hydrogen atom, a halogen atom,
, alkyl group, alkoxy group or acylamino
represents a group, R¹¹and R¹²are in adjacent positions on the ring.
When R¹⁴as well as
R¹⁵Each of these may be the same or different;
represents an element, a hydrocarbon group or a substituted hydrocarbon,
R¹¹,R¹²,R¹³,R¹⁴and R¹⁵at least one of
In order to prevent the aforementioned compounds from migrating in the layer,
A group of sufficient size, i.e., a diffusion-resistant group, to
is included. The residue imparting diffusion resistance is the compound according to the present invention.
is a hydrophilic colloid commonly used in photographic materials.
in a diffusion-resistant form.
It is the basis. Generally carries linear or branched aliphatic groups
or a carbocyclic ring generally having from 8 to 20 carbon atoms
an organic compound capable of carrying a formula or a heterocyclic or aromatic group;
residues are preferably used for this purpose. this
These residues can be directly or indirectly attached to the rest of the molecule.
For example -NHCO-, -NHSO₂−, −NR− (here
R represents hydrogen or an alkyl group), -O-, -S
-or-SO₂- to connect via. Diffusion resistance
The residue given is a base analogy that further gives solubility in water.
sulfo group or carboxyl group (these are anionic
may be present in the form of a sample). Possible
The overall mobility depends on the molecular size of the compound.
To be determined, in some cases e.g. the molecule as a whole
is large enough, ``provides diffusion resistance.''
It is also sufficient to have a group with a shorter chain length as a
possible. Compounds within the range of general formulas (A) and (B)
It is a thing (Nuox)¹and (Nuox)²is a nucleophilic group
(Nu)¹and (Nu)², for example -CH- and -NH₂to
The compound being reduced and its synthesis method are from Germany.
Claimed priority with patent application No. P2654213
It is described in Belgian Patent No. 861241.
Ru. Represented by the above general formulas (A) and (B)
The production of the compound reduced by the corresponding reduction
substance, i.e., the formation of a nucleophilic group (Nu) in the non-oxidized state
The compound is purified in excess of a solvent such as refluxing ethanol with p-
by treatment with an oxidizing agent such as benzoquinone.
It can be done by For the synthesis of compounds of general formulas (A) and (B)
Other oxidizing agents suitable for use include methyl-
1,4-benzoquinone, 2,5-dimethyl-1,
4-benzoquinone, octyl-1,4-benzoqui
Non, dodecyl-1,4-benzoquinone, 2,
3,5-trimethyl-1,4-benzoquinone,
1,4-naphthoquinone, 2-methyl-1,4-na
Phthoquinone, 2-octyl-1,4-naphthoquino
2-dodecyl-1,4-naphthoquinone, 5,
8-methane-1,4-naphthoquinone, 9,10-o
-benzo-1,4-naphthoquinone, 2,6-dime
Chil-1,4-benzoquinone, 2,6-dichloro
-1,4-benzoquinone. Compounds represented by general formulas (A) and (B)
The method for synthesizing the product is described in JP-A-54-130927.
Ru. Compounds represented by (A) and (B) of the present invention
Specific examples of compounds include compounds listed in -1 below.
The oxidized products (hydrogen) of the compounds listed in -1 to -40 are
Compounds in which the droquinone moiety is oxidized to quinone) are listed.
It will be done. As the reducible dye releasing agent of the present invention, JP-A-53
−110828, German Patent Application (OLS) No. 3008588
The ones listed are also valid. As the oxidizable dye fixing agent of the present invention, JP-A-49
-111628, JP-A-51-63618, Rsearch
Disclosure 14447 (1976 No. 144), U.S. Patent No.
Described in No. 4108850 and Japanese Patent Publication No. 53-69033
Compounds are also effective. Quinone type used in the photographic material of the invention
Compounds (A) and (B) do not release dyes as they are.
Unexposed light caused by heating
The hydrophilic dye is transferred by image-wise reduction in the
The ability to emit image-like images must be acquired. This is explained in the above-mentioned US Pat. No. 3,980,479.
Compounds in reduced form as described in the book
compared to using photographic materials that contain
In comparison, fog formation during storage and development is considerably reduced.
It has the advantage of not being Examples of pigment moieties contained in the compounds of the present invention
are azo dyes, azomethine dyes, anthraquinones
Dyes, naphthoquinone dyes, styryl dyes, nitro
Pigments, quinoline dyes, carbonyl dyes, phthalosic dyes
Examples include groups such as anine dyes or their metal complex salts.
It will be done. As a dye precursor contained in the compound of the present invention
Typical examples include those that give pigment through hydrolysis.
Yes, for example, JP-A-48-125818, US patent
As stated in No. 3222196 and No. 3307947, etc.
Sea urchin, something like acylated auxochrome of pigment
(temporary short-wave dye). this
Acylation reduces the absorption of the dye during exposure.
By temporarily shortening the wavelength, these
When coating a color image forming agent mixed with a light-sensitive emulsion
In addition, desensitization due to light absorption can be prevented. Na
Oh, for this purpose, it is necessary to transfer the
The hue differs depending on whether it is present in the emulsion layer or in the emulsion layer.
It is also possible to use dyes such as Also pigment part
For example, carboxyl group, sulfonamide group
It can have a group that gives it water solubility.
Wear. For the diffusion-resistant reducible dye release agent of the present invention
Well, 1 Immobilized in a hydrophilic or hydrophobic binder
and only the released dye has mobility.
is necessary. 2. Excellent stability against heat and dye release aids,
Does not release image-forming dye until reduced
thing. 3. Easy to synthesize. The following characteristics are required. Dyes that can be used as image-forming dyes include azo colors.
base, azomethine dye, anthraquinone dye, naph
Toquinone dye, styryl dye, nitro dye, kino
Phosphorus dye, carbonyl dye, phthalocyanine dye
etc., and representative examples are shown by hue. In addition, this
These dyes are temporary dyes that can be restored during processing.
It can also be used in a form with a shorter wavelength. In the above formula, R₁₁~R₁₆are hydrogen atoms and a
alkyl group, cycloalkyl group, aralkyl group,
alkoxy group, aryloxy group, aryl group,
Cylamino group, acyl group, cyano group, hydroxyl group, a
Rukylsulfonylamino group, arylsulfonyl
Amino group, alkylsulfonyl group, hydroxya group
alkyl group, cyanoalkyl group, alkoxycarbo
Nylalkyl group, alkoxyalkyl group, aryl group
hydroxyalkyl group, nitro group, halogen atom,
sulfamoyl group, N-substituted sulfamoyl group,
Carbamoyl group, N-substituted carbamoyl group, acyl
hydroxyalkyl group, amino group, substituted amino
group, alkylthio group, and arylthio group.
represents the identified substituents, and the alkali in these substituents
The kill group and the aryl group further include a halogen atom,
hydroxyl group, cyano group, acyl group, acylamino group,
Alkoxy group, carbamoyl group, substituted carbomoyl group
group, sulfamoyl group, substituted sulfamoyl group
group, carboxyl group, alkylsulfonylamino
group, arylsulfonylamino group or ureido group
may be replaced with . In the present invention, in combination with a reducible dye releasing agent,
In addition, an electron donor is used, and the heat subsequent to exposure
Development results in the imagewise release of mobile hydrophilic dyes.
It will be done. In other words, when the electron donor is heated, it
is exposed to light before reacting with the reducible dye-releasing agent.
An oxidation-reduction reaction occurs with silver halide, resulting in an image-like appearance.
The remaining electron donor is then reduced to
Reacts with dye release agents. Therefore reducible dye release
The hydrophilic potential of the agent increases as an inverse function of the destruction of the electron donor.
Able to release mobile dyes. In this specification
When the term “electron donor” is used, this must be photographed.
Reacts with various reducible dye-releasing agents contained in the base
and a nucleophilic precursor of the reducible dye-releasing agent.
- means a compound that can transfer electrons to a group
ing. The electron donor is a silver halide exposed to light.
The reaction rate between this and the reducible dye releasing agent is
It needs to be faster than the reaction rate. Like
or redox half-life time (hereinafter referred to as redox t1/2)
), evaluate the electron donor and halogenation
The reaction rate of silver is an electron donor and a reducible dye releasing agent.
at least 5 times, preferably 10 times the reaction rate with
In this case, the mobile component becomes image-like.
Selectively released. For such an electron donor
is ascorbic acid, trihydroxypyrimidine
For example, 2-methyl-4,5,6-trihydroxy
Cypyrimidine and hydroxylamine such as diethylamine
There is methylhydroxylamine. In certain preferred examples, the electron donor is an electron transfer agent.
(referred to as ETA in this specification)
I can stay. Generally, under processing conditions, ETA
A much better silver halide developer than a child donor.
a compound whose electron donor is a halogen
It is impossible to develop the silver or
has become substantially ineffective for its purpose.
ETA develops the silver halide and destroys it.
gives the corresponding image-like pattern of the electron donor
fulfills the function of This means that the oxidized ETA
This is because they easily accept electrons from electron donors.
Ru. Generally, the combination of an electron donor and a useful ETA
If ETA is used, electron donation is possible without using ETA.
The same processing compared to when only the body was used for processing.
Fast against silver halide under conditions
Gives development speed. In a highly preferred example,
ETA together with reducible dye release agents provides slow redox
st1/2, which is at least a reducible dye
Redox t1/ of electron donor used with releasing agent
2, preferably at least 10 times slower;
This example shows how to obtain optimal silver halide development speed.
while allowing a high degree of freedom for reducible dye release agents.
offers the freedom to obtain the optimal release rate when using
provide Among the ETA compounds that are useful from this point of view are
Also typical ETA compounds are hydroquinone compounds
substances such as hydroquinone, 2,5-dichlorohydrochloride
Droquinone and 2-chlorohydroquinone;
Nophenol compounds such as 4-aminophenol
, N-methylaminophenol, 3-methyl-
4-aminophenol and 3,5-dibromoamine
Nophenol; catechol compounds e.g. catechol
, 4-cyclohexylcatechol, 3-methoxy
Cicatechol and 4-(N-octadecylamino)
Catechol; phenylenediamine compounds, e.g.
N,N-diethyl-p-phenylenediamine, 3
-Methyl-N,N-diethyl-p-phenylenedi
Amine, 3-methoxy-N-ethyl-N-ethoxy
C-p-phenylenediamine and N,N,N′,
N'-tetramethyl-p-phenylenediamine
be. In a particularly preferred example, ETA is 3-pyrazo
Lydone compounds, such as 1-phenyl-3-pyrazo
Lydon, 1-phenyl-4,4-dimethyl-3-
Pyrazolidone, 4-hydroxymethyl-4-methy
-1-phenyl-3-pyrazolidone; 1-m-
Tolyl-3-pyrazolidone, 1-p-tolyl-3
-pyrazolidone, 1-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-pyrazo
Lydone, 1-(3-chlorophenyl)-4-methyl
-3-pyrazolidone, 1-(4-chlorophenyl)
-4-methyl-3-pyrazolidone, 1-(3-k)
rolophenyl)-3-pyrazolidone, 1-(4-k)
rolophenyl)-3-pyrazolidone, 1-(4-t)
lyl)-4-methyl-3-pyrazolidone, 1-(2
-tolyl)-4-methyl-3-pyrazolidone, 1
-(4-tolyl)-3-pyrazolidone, 1-(3-
tolyl)-3-pyrazolidone, 1-(3-tolyl)
-4,4-dimethyl-3-pyrazolidone, 1-
(2-trifluoroethyl)-4,4-dimethyl-
3-pyrazolidone and 5-methyl-3-pyrazoli
There is a don. Disclosed in U.S. Patent No. 3,039,869
Various ETA combinations can also be used, such as
can. Such developing agents are liquid processing compositions.
It can be used in at least one
part of any one or more layers of photographic elements or film uniforms.
It can also be included in the layer of the tube. For example,
In the silver halide emulsion layer, in the dye image-providing substance, in the intermediate
It can be used in the image receiving layer. Which
Of course, whether you should choose such an ETA depends on the process.
What kind of electron donor and reducible color
whether an elementary release agent is used and what photographic requirements are required;
Determined by the conditions under which the element is processed.
I can't stand it. Photographic elements of the invention include reducible dyes of the invention.
Preferably, the releasing agent is used in conjunction with an electron donor.
Yes. Separated yellow, magenta and cyan image dyes
In a multicolor photographic element having a donor layer unit,
To prevent color mixing, separate each layer unit.
Using a scavenger in the intermediate layer to be separated
is preferable. To reduce color mixing, oxidation
or a mobile or partially mobile compound in reduced form.
It is possible to use a suitable scavengeer for
can. In a preferred example, in a layer unit, a partial
fully or fully ballasted electron donor
Effective separation can be achieved by including
can. A substantially immobile electron donor is used.
interlayer diffusion is effectively reduced when However, if the compound is active in the layer unit,
A reducible color that remains and is in close contact with it
Transfer electrons to elementary-emitting compounds. After the imaging process is substantially completed,
amount of electron donor migrates to the adjacent layer unit.
Even if the
I won't give it. When a very high degree of image state identification is required
(e.g. multicolor photographic elements) may be decomposed by heating.
The electron donor precursors obtained are
used in combination with original dye-releasing compounds.
Generally, electron donor precursor to electron donor
The decomposition of occurs at a finite rate, and the generated electric
A child donor is formed during the silver halide development reaction.
The oxidation state of the electron transfer agent (ETA) or the developable
Reacts immediately with silver halides that can be used. In this reaction system, ETA is regenerated and
It is possible to develop a large amount of silver halide.
and electron donation in the area where development is occurring.
The body produces each at the same rate as it is produced by decomposition.
It has been destroyed. In this way, by decomposition
The generated electron donor reacts with the reduced raw dye releasing agent.
In order to
and here a mobile photographically useful group, e.g.
Releases image dye. In the most preferred case, heating
The electron donor precursor, which can be decomposed by
to implement it when used in multicolor photographic elements.
Contains sufficient ballast groups to be qualitatively immobile.
I'm reading. Electron donor precursor that can be decomposed by heating
is used, the electron donor precursor
Decomposition rate to electron donor, release of reducible dye
Rate of release of mobile photographically useful groups from agents
Can be used for adjustment. This decomposition rate
degree, especially when small amounts of ETA are used.
However, it may affect the development speed of silver halide.
It can have a sound. Therefore, due to these heating
Precursors that can be decomposed by
As the redox t1/2 when used with the drug,
From redox t1/2 when used with ETA
Those that give a long redox t1/2, e.g.
5 seconds or more for each reducible dye releasing agent.
Preferably one that is longer than 10 seconds is generally used.
Ru. Combination of electron donor and reducible dye-releasing compound
The rate of Ross oxidation plays a role in the release of photographically useful groups.
You need to understand that it can be used for clause steps.
There is a point. Electrodonors are generally electrical donors in photographic elements.
body: reducible dye releasing agent = 1:2 to 6:1 ratio,
Preferably they are used in a ratio of 1:1 to 2:1. In one preferred example, electrons that can be decomposed upon heating
The donor precursor has the following formula:
It is. Here, A together with the rest of the above formula represents 5 to 6 atoms.
Represents a group containing the atomic group necessary to form an aromatic ring.
and preferably a carbocyclic aromatic ring,
R³0 is a hydrogen atom or 1 containing 1 to 30 carbon atoms
or more, preferably said compound in a photographic manner.
To make it immobile in the bare binder layer
groups of sufficient size, e.g. containing 8 to 30 carbon atoms
group, which is an N-substituted carbamoyl group such as N-
Alkyl carbamoyl, alkyl thioether
groups, N-substituted sulfamoyl groups, e.g.
Rusulfamoyl, alkoxycarbonyl group, etc.
contains, and R³¹is a position containing 1 to 30 carbon atoms.
substituted or unsubstituted alkyl group, or 6-
Substituted or unsubstituted containing 30 carbon atoms
The aryl group is preferably a methyl group. This formula
Typical useful compounds within the range include:
There is: In other examples, other, decomposable electrons when heated
Donors can be used. for example, In yet another example, the electron donor exists in the keto form.
can be done. For example, protohydroquinone
form, which can be enolized in a base to become an electron donor
It forms the This type of compound is
It is as follows. In yet another example, the precursor, but not the
be at least semi-immobile in the layer of true elements.
preferable. A typical compound of this type is
It is as follows. In yet another example, The above electron donor precursor becomes a base when heated.
If there is, it decomposes on heating to low temperatures.
It's advantageous. Electron used with the reducible dye releasing agent of the present invention
In addition to the above ED-1 to ED-23, rice can be used as a donor.
National patent number 4263393, same number 4278750, German patent issued
Also listed in Application (OLS) No. 3006268
It is valid. The reducible dye releasing agent of the present invention is disclosed in US Pat.
Photosensitized by a known method such as the method described in No. 2322027.
It can be introduced into the layer of material. In that case below
Using high boiling point organic solvents and low boiling point organic solvents as shown below.
can be done. For example, phthalic acid alkyl ester (dibutyl
phthalate, dioctyl phthalate, etc.), phosphoric acid
Esters (diphenyl phosphate, triphenyl
phosphate, tricresyl phosphate, di-
octyl butyl phosphate), citric acid ester
(e.g. acetyl tributyl citrate), rest
Fragrant ester (octyl benzoate), alkylua
(e.g. diethyl laurylamide), fatty acids
Esters (e.g. dibutoxyethyl succinate)
(dioctyl azelate), trimesic acid ester
high
Boiling point organic solvent or organic solution with a boiling point of approximately 30°C to 160°C
solvents, such as lower acetates such as ethyl acetate and butyl acetate.
Rukyl acetate, ethyl propionate, secondary butyl acetate, ethyl propionate,
Chyl alcohol, methyl isobutyl ketone, β-
Ethoxyethyl acetate, methyl cellosolver
After dissolving in acetate, cyclohexanone, etc.,
Dispersed in aqueous colloids. The above high boiling point organic solutions
A mixture of the solvent and the low boiling point organic solvent may be used.
stomach. Also described in Special Publication No. 51-39853 and Japanese Patent Publication No. 51-59943.
Dispersion methods using the listed polymers can also be used.
In addition, a reducible dye-releasing agent can be dispersed in a hydrophilic colloid.
Various surfactants can be used when
These surfactants include those listed in this specification.
By the way, you can use the surfactants listed above.
can. The amount of high boiling point organic solvent used in the present invention is
10g or more per 1g of reducible dye releasing agent
Below, preferably 5g or less. Silver halides used in the present invention include silver chloride,
Silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, chloriodide
There are silver oxides, silver iodides, etc. In the present invention, without using an organic silver salt oxidizing agent
When silver halide is used alone, the grain
Uses silver halide containing some silver iodide crystals.
Preferably. Such silver halide
is the pattern of pure silver iodide as its X-ray diffraction pattern
This shows that. Photographic materials contain two or more types of halogen atoms.
Silver halide containing silver is used, but ordinary halogen
In emulsions, silver halide grains form perfect crystals.
It's on. For example, in silver iodobromide emulsions, the X-ray radiation
When measuring the folds, the patterns of silver iodide crystals and silver bromide crystals were found.
The X-ray diffraction pattern does not appear, and the X-ray diffraction pattern appears at a position corresponding to the mixing ratio.
A turn appears. In the present invention, particularly preferred silver halide is
Contains silver iodide crystals in the grains, so silver iodide
Silver chloroiodide, iodobromide that shows a crystalline X-ray pattern
Silver, silver chloroiodobromide. Such silver halide is, for example, silver iodobromide.
Add silver nitrate solution into potassium bromide solution
By doing this, silver bromide grains are first made, and then iodine is added.
It is obtained by adding potassium chloride. Silver halide size and/or halogen composition
Two or more types with different compositions may be used together. Grain size of silver halide used in the present invention
has an average particle size of 0.001 μm to 10 μm, and is preferably
Preferably, it is 0.001 μm to 5 μm. The silver halide used in the present invention can be used as is.
However, in addition, sulfur, selenium, tellurium, etc.
compounds, gold, platinum, palladium, rhodium and iris
Chemical sensitizers such as compounds such as dium, halogens
The use of reducing agents such as tin chloride or a combination of these
It may be chemically sensitized. For more information, see “The
Theory of the Photographic Process”4
Edition, written by T.H. James, Chapter 5, pages 149-169.
has been done. A particularly preferred embodiment of the present invention is an organic silver
In this case, it is combined with a salt oxidizing agent.
The silver halide used is silver halide alone.
When used, it has the characteristic of containing pure silver iodide crystals.
It is not necessarily necessary to have a
Use all known silver halides
I can do it. The organic silver salt oxidizing agent used in the present invention is photosensitive.
in the presence of silver halide at a temperature of 80°C or higher, preferably
The above image shape is
or, if necessary, image-forming material to coexist with the vertebrae.
It reacts with a reducing agent to form a silver image.
Ru. By coexisting with an organic silver salt oxidizing agent, higher
A photosensitive material that develops color with high density can be obtained. Examples of such organic silver salt oxidizing agents include
There are silver salts of organic compounds that have a boxyl group.
Among them, typical examples include fatty acid carboxylic acids.
There are silver salts and aromatic carboxylic acid silver salts. Examples of aliphatic carboxylic acids include silver behenic acid
salt, silver salt of stearic acid, silver salt of oleic acid,
Silver salt of liuric acid, silver salt of capric acid, myristicin
Silver salts of acids, silver salts of palmitic acid, silver salts of maleic acid
salt, silver salt of fumaric acid, silver salt of tartaric acid, 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 acetic acid, silver salt of butyric acid, silver salt of camphoric acid
etc. In addition, halogen atoms and hydrogen atoms in these silver salts
Those substituted with a loxyl group are also effective. Aromatic carboxylic acids and other carboxyl groups
Silver salts of compounds include benzoic acid silver salts, 3,
Silver salt of 5-dihydroxybenzoic acid, o-methylbenzoic acid
Silver salt of zoic acid, silver salt of m-methylbenzoic acid, p-
Silver salt of methylbenzoic acid, 2,4-dichlorobenzoic acid
silver salt of acid, silver salt of acetamidobenzoic acid, p-fluoride
silver salts of substituted benzoic acids, such as silver salts of enylbenzoic acid;
Silver salt of gallic acid, silver salt of tannic acid, phthalic acid
silver salt, silver salt of terephthalic acid, silver salt of salicylic acid,
Silver salt of phenyl acid, silver salt of pyromellitic acid, USA
3-carboxyme described in Patent No. 3785830
Thyl-4-methyl-4-thiazoline-2-thione
Silver salts such as those described in U.S. Pat. No. 3,330,663
Fatty acid carvone with thioether group
There are silver salts of acids, etc. In addition, it has a mercapto group or a thione group.
There are silver salts of the compound and its derivatives. For example, 3-mercapto-4-phenyl-1,
Silver salt of 2,4-triazole, 2-mercaptobe
Silver salt of ndzimidazole, 2-mercapto-5-
Silver salt of aminothiadiazole, 2-mercaptobe
silver salt of ntthiazole, 2-(s-ethyl glycosyl)
silver salt of benzthiazole, s-alamide)
Kyl (alkyl group with 12 to 22 carbon atoms) thioglycol
thiolacetic acid, etc., as described in JP-A No. 48-28221.
dichloromethane such as silver salt of licolic acid and silver salt of dithioacetic acid.
Silver salt of thiocarboxylic acid, silver salt of thioamide, 5-
Carboxy-1-methyl-2-phenyl-4-thi
Silver salt of opyridine, silver mercaptotriazine
salt, silver salt of 2-mercaptobenzoxazole,
Silver salt of mercaptooxadiazole, U.S. Patent No.
Silver salts described in 4123274, for example 1,2,4
-3-amino mercaptotriazole derivative
Nor-5-benzylthio 1,2,4-triazole
silver salt, 3- described in U.S. Pat. No. 3,301,678
(2-carboxyethyl)-4-methyl-4-thia
Silver thione compounds such as silver salt of zolin-2-thione
It's salt. In addition, there are silver salts of compounds with imino groups.
Ru. For example, Special Publication No. 44-30270, Publication No. 45-18416
Silver of benzotriazole and its derivatives described in the report
salts, e.g. silver salts of benzotriazole, methyl base
Alkyl-substituted benzenes such as silver salts of zotriazole
Silver salt of triazole, 5-chlorobenzotriazo
Halogen-substituted benzotriazo such as the silver salt of
silver salt of butylcarboimide benzotriazo
Carboimide benzotriazo like silver salt of
silver salts of silver as described in U.S. Pat. No. 4,220,709.
1,2,4-triazole and 1-H-tetrazole
silver salt of ru, silver salt of carbazole, silver salt of saccharin
salts, silver salts of imidazole and imidazole derivatives, etc.
There is. In addition, in the present invention, the research disk
Written in Jiya Vo1.170, No.17029, June 1978
Organic metal salts such as silver salts and copper stearate
can also be used in the same way as the various silver salts mentioned above.
Ru. Two or more organic silver salt oxidizing agents can be used together.
come. In the present invention, a reducing agent may be used as necessary.
can be done. The reducing agent in this case is the so-called auxiliary
Developing agent, silver halide and/or organic silver salt
Oxidized by an oxidizing agent, and the oxidized product is no longer reduced.
Although it is not possible to reduce the original dye-releasing agent,
Can contribute to the reduction of the reducible dye-releasing agent in the exposed area
It is a compound. Useful auxiliary developers include hydroquinone, t-
Butylhydroquinone, 2,5-dimethylhydride
Alkyl-substituted hydroquinones such as quinone, carbon
Tecols, pyrogallols, chlorohydrogens
Halogen substitution such as non and dichlorohydroquinone
Hydroquinones, methoxyhydroquinone, etc.
Alkoxy-substituted hydroquinones, methylhydro
Polyhydroxybenzene derivatives such as xinaphthalene
I have a body. Furthermore, methyl gallate, ascorbic
acids, ascorbic acid derivatives, N,N'-di-(2
Hydroxylamine such as -ethoxyethyl)hydroxylamine
Roxylamines, 1-phenyl-3-pyrazoly
Don, 4-methyl-4-hydroxymethyl-1-
Pyrazolidones such as phenyl-3-pyrazolidone
, reductones, hydroxytetronic acids, etc.
Useful. Auxiliary developers can be used within a certain concentration range.
Wear. The useful concentration range is 0.0005x modulus for silver.
A particularly useful concentration range is
It is 0.001 times mole to 4 times mole. The thermal development process during heating of the present invention is clearly explained.
Although I am not familiar with it, I think of it as follows.
I can do it. Halogen that becomes photosensitive when light is irradiated onto photosensitive materials
A latent image is formed on the silver oxide. Regarding this,
“The Theory of the
Photographic Process” 3rd Edition page 105~
It is described on page 148. Furthermore, by heating the photosensitive material, the exposure
photosensitive silver halide and a reducing electron transfer agent.
and/or an oxidation-reduction reaction occurs with the electron donor.
A silver image is formed in the exposed area, and the electron transfer agent and/or
The electron donor is oxidized. On the other hand, in the unexposed area
In this case, the reducible dye-releasing agent is released into the silver painting by heating.
The remaining electron transfer agent and/or as an inverse function of the image
Or it is reduced as a result of reacting with an electron donor and becomes a reduced form.
Then, this reduced reducible dye releasing agent is released.
It splits and releases the pigment. In this case, nucleophiles coexist
This accelerates the dye release reaction. organic silver salt oxidation
When using drugs together, start the reaction quickly.
Silver halide and organic silver salt oxidizing agent are
must be at a substantially effective distance.
Therefore, silver halide and organic silver salt oxidizing agents are the same.
Preferably, it is present in the second layer. Development by heating is different from so-called wet development.
This limits the diffusion of reactant species, so the reaction takes less time.
It takes time. However, heating for development
If you take too long, a thermal reaction may occur in the unexposed areas.
cannot be ignored, causing so-called fog.
It's not right. The present invention aims to improve these inconveniences.
One way to do this is to use hot solvents.
I can do that. Here, "thermal solvent" means
solid at the temperature, but depending on the heat treatment temperature used or
together with other components at lower temperatures
Refers to non-hydrolyzable organic materials that exhibit mixed melting points.
However, if a latent image is heated in the presence of a hot solvent, it will not be developed.
Faster speed and better image quality
I can do it. Such a hot melt used in the present invention
Examples of agents include compounds that can serve as solvents for developing agents, and
It is possible to promote the physical phenomenon of silver salt with dielectric constant material.
Known compounds are useful. useful heat
As a solvent, the polyester described in U.S. Pat. No. 3,347,675 is used.
Glycols, e.g. average molecular weight 1500-20000
Polyethylene glycol, polyethylene oxy
Derivatives such as oleic acid esters, beeswax,
Monostearin, −SO₂−, −CO− group-containing polymers
Compounds with dielectric constant, e.g. acetamide, succine
imide, ethyl carbamate, urea, methyls
Sulfonamide, ethylene carbonate, US patent
Polar substance described in No. 3667959, 4-hydroxybutylene
lactone of tananoic acid, methylsulfinylmethane,
Tetrahydrothiophene-1,1-dioxai
Research Disclosure December 1976
1,10-decanediol described on pages 26 to 28 of the issue
Methyl nitrate, biphenyl suberate, etc. are preferred.
Often used. The role of the hot solvent in the present invention is not necessarily clear.
However, it promotes the diffusion of reactive molecular species during development.
is understood to be the main role. Photosensitive silver halide, organic silver salt oxidizing agent of the present invention
are arranged in the binder below. Also, reducibility
A dye release agent is also dispersed in the binder described below. The binder used in the present invention can be used alone.
or can be used in combination. This bar
A hydrophilic material can be used for the inder.
Ru. As a hydrophilic binder, transparent or translucent
Hydrophilic colloids are typical, such as gelatin
tanning, gelatin derivatives, cellulose derivatives, etc.
Proteins, starch, gum arabic, pullulan,
Dextrin etc. are combined with natural substances such as polysaccharides and polysaccharides.
Rivinyl alcohol, polyvinylpyrrolidone, a
Water-soluble polyvinyl compounds such as acrylamide polymers
Contains synthetic polymeric substances such as. Other synthetic polymer compounds
In the form of latex, especially the size of photographic materials
There are dispersed vinyl compounds that increase stability. The silver halide used in the present invention has a methine color.
It may also be spectrally sensitized by other elements. use
The pigments include cyanine pigments and merocyanine pigments.
base, complex cyanine dye, complex merocyanine dye,
Holopolar cyanine dye, hemicyanine dye,
Includes styryl dyes and hemioxonol dyes.
It will be done. Particularly useful dyes include cyanine dyes,
Belongs to anine pigments and complex merocyanine pigments
It is a pigment. These pigments contain a basic heteroartic ring.
Nucleus normally used for cyanine pigments as a nucleus.
Misalignment can also be applied. i.e. pyrroline nucleus, oxa
Zolin nucleus, thiazoline nucleus, pyrrole nucleus, oxazo
ole nucleus, thiazole nucleus, cenarezole nucleus, imida
Sol nucleus, tetrazole nucleus, pyridine nucleus, etc.;
a nucleus in which an alicyclic hydrocarbon ring is fused to the nucleus;
A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e.
indolenine nucleus, benzindolenine nucleus, india
alcohol nucleus, benzoxadol nucleus, naphthoxazo
core nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, benzimidazole
Nucleus, quinoline nucleus, etc. can be applied. These cores are charcoal
It may be substituted on an elementary atom. For merocyanine pigments or complex merocyanine pigments
is a pyrazoli as a core with a ketomethylene structure.
ion-5-one nucleus, thiohydantoin nucleus, 2-thio
Oxazolidine-2-,4-dione nucleus, thiazolidine
Dine-2,4-dione nucleus, rhodanine nucleus, thiova
Apply 5- to 6-membered heterocyclic nuclei such as rubituuric acid nuclei.
be able to. Useful sensitizing dyes include, for example, German patent no.
929080, U.S. Patent No. 2231658, U.S. Patent No. 2493748
No. 2503776, No. 2519001, No. 2519001, No. 2503776, No. 2519001, No.
No. 2912329, No. 3656959, No. 3672897, No.
No. 3694217, No. 4025349, No. 4046572,
British Patent No. 1242588, Special Publication No. 14030/1973, No. 52
−24844 can be mentioned.
Ru. These sensitizing dyes may be used alone, but
Combinations of sensitizing dyes may also be used.
is often used especially for the purpose of supersensitization.
Representative examples are U.S. Patent No. 2688545 and U.S. Patent No. 2977229.
No. 3397060, No. 3522052, No. 3522052, No. 3397060, No. 3522052, No.
No. 3527641, No. 3617293, No. 3628964, No.
No. 3666480, No. 3672898, No. 3679428,
Same No. 3703377, Same No. 3769301, Same No. 3814609,
No. 3837862, No. 4026707, British Patent No.
No. 1344281, No. 1507803, Special Publication No. 43-4936,
No. 53-12375, JP-A No. 52-110618, No. 52-
Described in No. 109925. Together with the sensitizing dye, it itself has a spectral sensitizing effect.
No pigments or materials that do not substantially absorb visible light
The emulsion contains a substance that exhibits supersensitization.
But that's fine. For example, substituted with a nitrogen-containing heterocyclic group
aminostyl compounds (e.g. U.S. Pat. No. 2,933,390)
No. 3635721), aromatic organic acids
Formaldehyde condensates (e.g. U.S. Pat.
3743510), cadmium salt, azai
It may also contain an endene compound or the like. US Patent No.
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3,635,721 is particularly useful. In the present invention, various dye release aids are used.
method, e.g. any layer or color in a photosensitive material
Containing it in any layer of the base fixing material
It can be used by Dye release aid and
is an electron transfer agent and/or electron donor and reducibility.
Promotes or inhibits redox reactions with dye releasing agents.
Oxidized and reduced in the subsequent dye release reaction
Acts nucleophilically on the dye-releasing agent to promote dye release.
base or base precursor
is used. In the present invention, in order to promote the reaction,
Therefore, it is especially useful to use these dye release aids.
However, these dye release aids are not included in light-sensitive materials.
In the case of containing
It is necessary to specifically select those that do not grow. Preferred bases that can be used in photosensitive materials
Examples include amines,
Realkylamines, hydroxylamines, fats
Aliphatic polyamines, N-alkyl substituted aromatic amines
N-hydroxyalkyl-substituted aromatic amines
and bis[p-(dialkylamino)pheni
] Methanes can be mentioned. Also US patent
No. 2410644 includes betaine tetramethyl iodide
Ammonium, diaminobutane dihydrochloride
U.S. Pat. No. 3,506,444 describes urea, 6-a
Organic compounds containing amino acids such as minocaproic acid
Things are described and useful. The base precursor is heated
It releases more basic components. Typical
Examples of base precursors are described in UK Patent No. 998949.
ing. Preferred base precursors are carboxylic acids and
It is a salt of a basic base, and is a useful carboxylic acid.
Lichloroacetic acid, trifluoroacetic acid, useful bases
Guanidine, piperidine, morpholine, p-
Examples include toluidine and 2-picoline. US Patent No.
The guanidine trichloroacetic acid described in No. 3220846 is
It is useful for Also mentioned in the Publication of JP-A No. 50-22625
Aldonamides, which are used in
, and is preferably used. These dye release aids can be used in a wide range of applications.
I can do it. A useful range is the dry film coating of photosensitive materials.
Less than 50% by weight, preferably
It ranges from 0.01% to 40% by weight. In particular, the heat-developable photosensitive material of the present invention has the following general formula:
Development is accelerated and the dye is
It is also advantageous to promote the release of . [General formula] In the above formula, A₁,A₂,A₃,A_Fourare the same or different
hydrogen atoms and alkyl atoms, respectively.
group, substituted alkyl group, cycloalkyl group, aral
Kyl group, aryl group, substituted aryl group and heterocycle
Represents a substituent selected from among the residues, and A₁and
A₂Or A₃and A_Fourmay be connected to form a ring.
stomach. As a specific example, H₂NSO₂N.H.₂,H₂NSO₂N
(CH₃)₂,H₂NSO₂N(C₂H_Five)₂,H₂NSO₂NHCH₃,
H₂NSO₂N(C₂H_FourOH)₂,C.H.₃NHSO₂NHCH₃, etc. The above compounds can be used in a wide range of applications. The useful range is the dry coated film of the photosensitive material converted into weight.
20% by weight or less of the calculated amount, more preferably,
It is 0.1-15% by weight. In the present invention, when a water-releasing compound is used, the dye is released.
This is advantageous because the reaction is accelerated. Water-releasing compounds are compounds that decompose and release water during thermal development.
It refers to the compound that is emitted. These compounds are
Known for its transfer printing of fibers, published in Japanese Patent Application Publication No. 1983-
NH described in Publication No. 88386_FourFe(SO_Four)₂・12H₂There is O etc.
It is for use. The support of the photosensitive material used in the present invention is
It is capable of withstanding temperature. general
Supports include glass, paper, metal and similar materials.
Acetyl cellulose is not only used by the body, but also
Zufilm, cellulose ester film, poly
Vinyl acetal film, polystyrene film
film, polycarbonate film, polyethylene film
Refthalate films and related films
lum or resin material. US Patent No.
The polyester described in No. 3634089 and No. 3725070 is
Preferably used. Particularly preferably polyethylene
A lenterephthalate film is used. The coating liquid used in the present invention is prepared separately.
Using the synthesized silver halide and organometallic salt oxidizing agent,
It is also possible to prepare the solution by mixing it before use.
However, it is also possible to mix the two and mix them in a ball mill for a long time.
It is also effective to combine Also prepared organic silver salt
By adding a halogen-containing compound to the oxidizing agent, organic silver salt
Method of forming silver halide with silver in an oxidizing agent
is also valid. The production of these silver halides and organic silver salt oxidizing agents
For details on how to mix the two, please refer to the resource.
Chi Disclosure No. 17029 and JP-A-1973-
No. 32928, No. 51-42529, U.S. Patent No. 3700458,
Described in JP-A-49-13224, JP-A-50-17216, etc.
ing. In the present invention, photosensitive silver halide and organic
The amount of silver salt oxidizing agent applied is 50 mg in total in terms of silver.
~10g/m²is appropriate. Photographic emulsion layer or other hydrophilicity of the light-sensitive material of the present invention
The colloid layer contains coating aids, antistatic agents, and slippery additives.
Good, emulsification and dispersion, prevention of adhesion and improvement of photographic properties (e.g.
For various purposes such as acceleration of development, high contrast, and sensitization)
Various surfactants may also be included. For example, saponins (steroids), alkylene
Oxide derivatives (e.g. polyethylene glycol)
polyethylene glycol/polypropylene
Recall condensate, polyethylene glycol alkyl
ethers or polyethylene glycol alkyl
Ruaryl ethers, polyethylene glycol
Esters, polyethylene glycol sorbitan
Esters, polyalkylene glycol alkyl
Amine or amide, silicone polyethylene
oxide adducts), glycidol derivatives (e.g.
For example, alkenyl succinic polyglycerides, alky
ruphenol polyglyceride) of polyhydric alcohol
Fatty acid esters, sugar alkyl esters, etc.
Nonionic surfactant; alkyl carboxylate,
Alkyl sulfonate, alkylbenzene sulfonate
phosphate, alkylnaphthalene sulfonate, alkylnaphthalene sulfonate,
Kill sulfate esters, alkyl phosphate esters
N-acyl-N-alkyltaurines, sulfur
Phosuccinic acid esters, sulfoalkyl polyoxy
Cyethylene alkyl phenyl ethers, polio
Such as xyethylene alkyl phosphate esters, etc.
Carboxy group, sulfo group, phosphor group, sulfuric acid ester
Animated groups containing acidic groups such as ester groups and phosphoric acid ester groups.
On surfactant; amino acids, aminoalkyls
Sulfonic acids, aminoalkyl sulfates or phosphates
Tels, alkyl betaines, amine oxides
Amphoteric surfactants such as; alkylamine salts, fats
Group or aromatic quaternary ammonium salts, pyryl
Heterocyclic quaternary anhydrides such as zinium and imidazolium
monium salts, and phosphorus containing aliphatic or heterocycles.
Cation interfaces such as honium or sulfonium salts
Activators can be used. Among the above surfactants, ethylene oxide is present in the molecule.
polyethylene with oxide repeating unit
Containing recall type nonionic surfactants in photosensitive materials
It is preferable to let them. Especially preferably ethylene
Those with 5 or more repeating units of oxide
desirable. Nonionic surfactants that meet the above conditions are
It is widely used outside the field, and its structure is
The structure, properties, and synthesis method are publicly known. Typical
Publicly known documents include Surfactant Science Series
Volume 1.Nonionic Surfactants (Edited by
Martin J. Shick, Marcel Dekker Inc.1967),
Surface Active Ethylene Oxide Adducts
(Schoufeldt.N, Pergamon Press 1969) etc.
and the nonionic surfactants described in these documents.
Those satisfying the above conditions are preferably used in the present invention.
I can stay. These nonionic surfactants can be used alone,
It can also be used as a mixture of two or more types. Polyethylene glycol type nonionic surfactant
is equal to or less than the weight of the hydrophilic binder, preferably
or less than 50%. The photosensitive material of the present invention has a pyridinium salt.
It can contain cationic compounds. Pili
An example of a cationic compound with a zinc group is
PSA Journal, Section B36 (1953),
USP2648604, USP3671247, Special Publication Showa 44-30074,
It is described in Special Publication No. 44-9503, etc. The photosensitive material used in the present invention has development activation.
At the same time, it is possible to use compounds that stabilize images.
I can do it. Among them, U.S. Patent No. 3301678
2-Hydroxyethylisothiuroniur,
Isothiuronium represented by lichloroacetate
1,8-(3,
6-dioxaoctane)bis(isothiuronium)
bisisothiuronates such as mu-trifluoroacetate)
Tiho described in West German Patent No. 2162714
compounds, 2-A described in U.S. Pat. No. 4,012,260
Mino-2-thiazolium trichloroacetate
2-Amino-5-bromoethyl-2-thiazo
Thiazolium such as trichloroacetate
Compounds, bis(2) described in U.S. Pat. No. 4,060,420
-amino-2-thiazolium)methylenebis(sulfur)
sulfonylacetate), 2-amino-2-thiazo
Lium phenyl sulfonylacetate etc.
has α-sulfonylacetate as the acidic moiety.
Compounds described in U.S. Pat. No. 4,088,496,
It has 2-carboxycarboxamide as its sexual part.
Compounds etc. are preferably used. In the case of the present invention, the reducible dye releasing agent is colored.
This further prevents irradiation and flakes.
- Add anti-shrinking substances or various dyes to photosensitive materials.
Although it is not so necessary to include it in the
In order to improve the sharpness of the image, the
No. Publication, U.S. Patent No. 3253921, U.S. Patent No. 2527583,
As stated in each specification such as No. 2956879,
Containing filter dyes, absorbent substances, etc.
I can do it. Also, some of these dyes are thermally decolorizable.
For example, US Pat. No. 3,769,019;
As stated in No. 3745009 and No. 3615432.
Una dye is preferred. The photosensitive material used in the present invention may be
Various additives known as heat-developable photosensitive materials
agents, and layers below the photosensitive layer, such as antistatic layers and conductive layers.
layer, protective layer, intermediate layer, AH layer, release layer, etc.
can be done. As various additives,
Ji Disclosure Magazine Vol.170, June 1978
Additives listed in No. 17029 of
Plastics, sharpness improving dyes, AH dyes, sensitizing dyes,
Matting agent, surfactant, optical brightener, anti-fading agent
There are additives such as In the present invention, as with the heat-developable photosensitive layer, protective
layer, intermediate layer, undercoat layer, back layer and other layers.
However, you can prepare each coating solution and use the immersion method or air
- Knife method, curtain coating method or U.S. patent no.
Hopper coating method described in specification No. 3681294, etc.
Sequentially coat onto a support using various coating methods and dry.
Photosensitive materials can be made by this process. Furthermore, if necessary, please refer to US Pat. No. 2,761,791 and
and those described in British Patent No. 837095.
Applying two or more layers at the same time depending on the method
You can also do it. In the present invention, the photosensitive material obtained after exposure to light is
For example, the latent image is
Approximately 0.5 seconds to approximately 300 seconds at moderately elevated temperature.
Developing can be done by heating the entire element.
can. If the temperature is within the above range, heating
By increasing or shortening the time, both high and low temperature
It can also be used in both cases. Especially about 110℃~approx.
A temperature range of 160°C is useful. As the heating means
It is not just a hot plate, iron, hot roller or car.
A heating element using a bong or titanium white, or
Using ordinary means such as methods using analogs thereof.
I can do that. Mobility under high temperature conditions in the presence of hydrophilic thermal solvents
The image created by the hydrophilic dye is transferred to the dye fixing layer.
In the image forming method of the present invention, a mobile dye is used.
Even if the migration of the dye begins simultaneously with the release of the dye,
It may be after the release of Therefore, moving
Heating for processing is not necessary even after heat development.
It may be done at the same time as development. At the same time as heat development
This means that the heat for development is emitted at the same time.
It also acts as a heating element for the movement of pigments.
means. Optimal temperature for development and dye migration
Optimum temperature and required heating time for each
do not necessarily match, so each temperature is measured independently.
You can also set the degree. Heating for dye migration improves the storage stability of photosensitive materials,
From the viewpoint of workability, etc., the temperature is between 60℃ and 250℃, so
In the present invention, in this temperature range, the hydrophilic heat soluble
Appropriately select a substance that acts as an agent.
I can do it. Hydrophilic hot solvents can be quickly heated
It is necessary to help the movement of crab pigments.
Of course, you should also consider the heat resistance of the photosensitive material.
Considering this, the melting point required for a hydrophilic thermal solvent is 40
°C to 250 °C, preferably 40 °C to 200 °C, more preferably
The temperature range is between 40℃ and 150℃. In the present invention, "hydrophilic thermal solvent" means
is in a solid state, but becomes a liquid state when heated
is a compound, (inorganic/organic) value > 1, and
Compounds with a solubility temperature in water of 1 or more at room temperature
defined. Inorganic and organic here refer to chemical compounds.
A concept for predicting the properties of things, and its details
For example, it is described in Chemistry Area 11, p. 719 (1957).
It is. Hydrophilic thermal solvents play a role in assisting the movement of hydrophilic dyes.
Since it has a certain ratio to hydrophilic dyes,
Preferably, it is a compound that can act as a solvent.
It is considered that Generally preferred as a solvent for dissolving organic compounds.
The (inorganic/organic) value of the solvent is
It is close to the (inorganic/organic) value of organic compounds.
known from experience. On the other hand, used in the present invention
(Inorganic/Organic) value of reducible dye releasing agent
is approximately 1, and these reducible dyes
The hydrophilic dye (inorganic/organic) released from the release agent
The (inorganic/organic) value of the reducible dye-releasing agent
and preferably has a value larger than the
It has a value of 1.5 or more, particularly preferably 2 or more.
Ru. The hydrophilic heat solvent used in the present invention has a hydrophilic color.
Only the dye is transferred, and the reducible dye-releasing agent is not transferred.
Since it is preferable to have something that does not
The (organic) value is the (inorganic/organic) value of the reducible dye release agent.
(organic) value is required. That is,
As a hydrophilic thermal solvent, the (inorganic/organic) value is
It is an essential condition that it is 1 or more, preferably
It is 2 or more. On the other hand, if we consider it from the perspective of molecular size, the transfer
Around the moving pigment, there is a mechanism that does not inhibit its movement and
It is considered preferable that there be molecules that can move from the
Select. Therefore, the molecular weight of hydrophilic thermal solvents is small.
more preferably about 200 or less, more preferably a molecular weight of about 200 or less
is approximately 100 or less. The hydrophilic thermal solvent of the present invention is produced by heat development.
The transfer of hydrophilic dyes to the dye fixed layer is substantially inhibited.
It is enough if it can help, so I added it to the dye fixing layer.
Not only can it be contained in the photosensitive layer, etc.
It can also be incorporated into the photosensitive material as a dye fixing layer.
It may be contained in both the photosensitive layer and the photosensitive layer.
Independent color in optical material or with dye fixing layer
An independent fixing material containing a hydrophilic heat solvent
It is also possible to provide layers. Adding the dye to the dye fixing layer
From the perspective of increasing transfer efficiency, hydrophilic heat-soluble
The agent is contained in the dye fixing layer and/or its adjacent layer.
It is preferable to Hydrophilic thermal solvents are usually dissolved in water to form a binder.
alcohols, e.g.
Can also be used by dissolving in tanol, ethanol, etc.
I can do it. The hydrophilic heat solvent used in the present invention is suitable for photosensitive materials and
5 to 500 weight of the total coated amount of dye-fixing material and/or dye-fixing material.
%, preferably 20-200% by weight, particularly preferably
A coating weight of 30 to 150% by weight can be used. Examples of the hydrophilic heat solvent used in the present invention include
Ureas, pyridines, amides, sulfonamides
imides, alcohols, oximes, etc.
Other heterocycles may be mentioned. Next, the specifics of the hydrophilic heat solvent used in the present invention are as follows.
Give an example. (34)CH₃S.O.₂N.H.₂, (35)HOCH₂S.O.₂N.H.₂ (36)H₂NSO₂N.H.₂, (37)₃HCNHSO₂N.H.₂ (45) (CH₃CO)₂N.H. (47)HOCH₂(CHOH)₃CH₂Oh, (48)CH₃C(CH₂OH)₃, (49)C₂H_FiveC(CH₂OH)₃ (50)O₂NC(CH₂OH)₃, (51) Sorbitsuto (54)HOCH₂−CH=CH−CH₂OH (55)CH₃CH=NOH, (56) HON=CHCH=NOH (58)HOCH₂CH＝NOH Among these, ureas (1), (2), (3), (10), pi
Lysines (17), (19), amides (26),
(30), (33), sulfonamides (34), (36),
Imides (40), (41), (43), (44) and alco
Particularly preferred are (46) and (54). Also, the original
The hydrophilic heat solvent used in the light must be used alone.
It is also possible to use two or more types together. In the present invention, the image exposure is performed simultaneously with the image exposure, or the image exposure
Image-wise generation due to the heating phenomenon that follows the light
This mobility causes the movement of hydrophilic mobile dyes.
A dye fixing layer that absorbs the dye and fixes the dye image.
is necessary. For this purpose, the photosensitive material of the present invention
At least silver halide, reducible color on the carrier
Release agent, binder and organic silver salt if necessary
A photosensitive layer containing an oxidizing agent and a hydrophilic layer formed by the layer
Pigments that can absorb mobile pigments
Consists of a fixed layer. With such a photosensitive layer
A dye fixing layer is a dye fixing layer that can be formed on the same support.
It can also be formed on separate supports.
Ru. Peel off the dye fixing layer and the photosensitive layer.
You can also do it. For example, uniform heat development after imagewise exposure
Then, peel off the dye fixing layer or photosensitive layer.
can be done. Also, a photosensitive layer is coated on the support.
The photosensitive material and the fixing layer were coated on the support.
If the fixing material is formed separately, the photosensitive material
After imagewise exposure and uniform heating of the material, it is possible to overlay the fixing material.
A mobile dye can be transferred to a fixed layer. Also, the feeling
Imagewise exposure of only the optical material, followed by a dye fixing layer
There is also a method of heating them uniformly by stacking them on top of each other. For example, for adhesion between the photosensitive material and the dye fixing material,
Normal methods such as pressure rollers can be used.
However, in order to ensure sufficient adhesion,
Heating can also be used in combination. Heat development after image exposure or at the same time as image exposure
After that, the surface of the photosensitive material and the dye-receiving material of the dye-fixing material are
When heating the surface in close contact with the surface, the heating will cause dye transfer.
It is sufficient to make it contribute only to the
From the viewpoint of heating temperature and heating time,
Can be set independently of heat. When this method is adopted, processing for development is required.
Heat should not contribute to dye migration as much as possible.
The reaction for development can be completed in a short time.
While it is preferable to
Heating to transfer the dye to the dye transfer layer is done in an appropriate manner.
The thermal reaction of the unexposed area is induced within the transfer time of
Keep the temperature as low as possible to prevent
is preferable to obtain clear images. The dye fixing layer may have a white reflective layer.
stomach. For example, on top of a mordant layer on a transparent support,
It is possible to provide a titanium dioxide layer dispersed in latin.
can. The titanium dioxide layer forms a white opaque layer.
This allows the transferred color image to be viewed from the transparent support side.
As a result, a reflective color image can be obtained. For dye transfer from the photosensitive layer to the dye fixed layer
A dye transfer aid may be used. dye transfer
Motivating agents include water, caustic soda, caustic potash, and inorganic
A basic aqueous solution containing an alkali metal salt is used.
It will be done. Also, methanol, N,N-dimethylform
Low boiling points such as amide, acetone, diisobutyl ketone, etc.
Point solvents, or these low boiling point solvents and water or basic
A mixed solution with an aqueous solution of is used. dye transfer aid
The agent may be used by wetting the image-receiving layer with a solvent.
In the material as crystal water and microcapsules,
You can also leave it in the internal organs. The dye fixing layer contains a dye mordant for fixing the dye,
Hydrophilic heat solvent to aid dye transfer, dye release
Base and/or base for promoting reaction, etc.
Precursors, etc., and also binders for binding these.
It can contain the following: The dye fixing layer is a photosensitive material
When provided on a support separate from the base material, the base
and/or a base precursor is particularly preferred.
This is a new embodiment. When the dye mordant is a polymer mordant,
This also works as a binder, so
In such cases, reduce the amount of binder or use binder.
There is no need to use a special radiator. On the contrary, Vine
When the agent also functions as a mordant,
Similarly, dye mordants can also be omitted.
Binders used in photosensitive materials
You can use the same type. The mordant used in the dye fixing layer of the present invention is usually
You can choose any mordant from among the mordants used.
Among them, polymer mordants are particularly preferred.
Delicious. Here, polymer mordants refer to secondary and tertiary mordants.
Polymers containing amino groups, nitrogen-containing heterocyclic moieties
Polymers with these quaternary cation groups
Containing polymers, etc., with a molecular weight of 5,000 to 200,000, especially
10,000 to 50,000. For example, U.S. Pat.
No. 2548564, No. 2484430, No. 3148061, No.
Vinyl resin disclosed in specification No. 3756814 etc.
Lysine polymer and vinylpyridinium cation
Polymer; U.S. Patent No. 3625694, U.S. Patent No. 3859096
No. 4128538, British Patent No. 1277453
Polymers that can be crosslinked with gelatin, etc., as disclosed in
Mordant; U.S. Patent No. 3958995, U.S. Patent No. 2721852
No. 2798063, JP-A-54-115228, No. 54
-145529, specification No. 54-126027, etc.
Aqueous sol-type mordant; US Pat. No. 3,898,088
Water-insoluble mordants disclosed in the specification;
Patent No. 4168976 (Japanese Unexamined Patent Publication No. 54-137333) Specification etc.
Reactions that can carry out covalent bonding with dyes disclosed in
Mordant; furthermore, U.S. Pat. No. 3,709,690;
No. 3788855, No. 3642482, No. 3488706, No. 3488706, No.
No. 3557066, No. 3271147, No. 3271148,
JP-A-50-71332, JP-A No. 53-30328, JP-A No. 52-
No. 155528, No. 53-125, No. 53-1024
The disclosed mordants, as well as U.S. Pat.
Mordant described in No. 2675316 and No. 2882156
can also be mentioned. Among these mordants, for example, gelatin, etc.
Water-insoluble mordant that cross-links
agents, and aqueous sol (or latex dispersion) media.
Dyes can be preferably used. Particularly preferred polymer mordants are shown below. (1) Has a quaternary ammonium group and is similar to gelatin.
Groups that can be covalently bonded (e.g. aldehyde groups, chloro
loalkanoyl group, chloroalkyl group, vinyl
Sulfonyl group, pyridinium propionyl group,
Vinyl carbonyl group, alkylsulfonoxy group
etc.) for example (2) Repeating monomers represented by the general formula below
Repeating units and other ethylenically unsaturated monomers
A copolymer consisting of
bisalkanesulfonate, bisalkanesulfonate
reaction product with honate).

[Formula] R ^b ₁ : H, alkyl group R ^b ₂ : H, alkyl group, aryl group Q: divalent group R ^b ₃ , R ^b ₄ , R ^b ₅ : alkyl group, aryl group, or R ^b ₃ ~ At least two of R ^b ₅ may be combined to form a heterocycle. X: Anion (The above alkyl groups and aryl groups include substituted ones.) (3) Polymer represented by the following general formula x: about 0.25 to about 5 mol% y: about 0 to about 90 mol% z: about 10 to about 99 mol% A: Monomer having at least two ethylenically unsaturated bonds B: Copolymerizable ethylenically unsaturated Monomer Q: N, P R ^b ₁ , R ^b ₂ , R ^b ₃ : Alkyl group, cyclic hydrocarbon group, or at least two of R ^b ₁ to ^{R b} ₃ may be combined to form a ring . (These groups and rings may be substituted.) (4) Copolymer consisting of (a), (b) and (c)

【formula】

[Formula] 3
Water-insoluble polymer having more than R ^b ₁ , R ^b ₂ , R ^b ₃ : Each represents an alkyl group, and the total number of carbon atoms in R ^b ₁ to ^{R b} ₃ 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, it is also possible to use gelatin manufactured by different methods such as lime-treated gelatin and acid-treated gelatin, or gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment. The mixing ratio of the polymer mordant and gelatin of the present invention and the coating amount of the polymer mordant 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. However, the mordant/gelatin ratio is 20/80 to 80/20 (weight ratio), and the amount of mordant applied is 0.5
Preferably it is used at ~8 g/ ^m2 . Typical dye fixing materials used in the present invention are:
It 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 protective layer can be further provided if necessary. As such a protective layer, one generally used as a protective layer for photosensitive materials can be used as is, but if the dye fixing layer is provided on the dye fixing material separately from the photosensitive material, In order not to inhibit the movement of the hydrophilic dye, it is preferable to impart hydrophilicity to the protective layer as well. The photographic light-sensitive material and dye-fixing material of the present invention include:
The photographic emulsion layer and other binder layers may contain an inorganic or organic hardener. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), activated vinyl compound (1,3,5
-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination. Further, as the heating means for moving the dye, various means similar to the heating means used in the heating phenomenon described above can be employed. In the present invention, similar to the heat-developable photosensitive layer, coating solutions are prepared for the dye fixing layer, protective layer, intermediate layer, undercoat layer, back layer, and other layers, and are applied using the dipping method, air knife method, curtain method, etc. A light-sensitive material can be prepared by sequentially coating on a support using a coating method or various coating methods such as the hopper coating method described in US Pat. 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, various exposure means can be used. The latent image is obtained by imagewise exposure to radiation, including visible light. Generally, light sources used for normal color printing include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, and CRTs.
A light source, a fluorescent tube, a light emitting diode, etc. can be used as the light source. The original drawing may be a line image such as a technical drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original drawing may be 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 can be directly transmitted to a CRT or
It is also possible to print the image on a heat-developable photosensitive material by exposing it to a FOT and then forming the image on a heat-developable photosensitive material either in close contact or through a lens. Furthermore, LEDs (light emitting diodes), which have recently seen significant progress, are being used as exposure means or display means in various devices. this
It is difficult to make LEDs that emit blue light effectively, so in order to reproduce color images using LEDs, three types of LEDs that emit green, red, and infrared light are used. Each portion of the photosensitive material that is sensitive to light may be designed to emit yellow, magenta, and cyan dyes. That is, the green-sensitive portion (layer) may contain a yellow dye-providing substance, the red-sensitive portion (layer) may contain a magenta dye-providing substance, and the infrared-sensitive portion (layer) may contain a cyan dye-providing substance. . Other combinations are 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 a memory such as a computer 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 and exposing the image. . 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,
Not only can the sensitivity of conventional silver halide photographic light-sensitive materials be maintained, but since the formed dye image is fixed to a dye fixing material, the quality and storage stability of the dye image are extremely good, and the color reproducibility is excellent. often,
Although it is a completely dry process, it is extremely useful because it can reproduce color images satisfactorily. 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 to hard images. Since the dye is fixed in the dye fixing layer, the image has good storage stability, so it can be easily used even when long-term storage is required, which is superior to conventional photographic technology. Therefore, the present invention has great significance. EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto. Emulsion Preparation Example 1 Preparation of Silver Iodobromide Emulsion Dissolve 40 g of gelatin and 26 g of KBr in 3000 ml of water, stir this solution while keeping it at 50°C, and then dissolve a solution of 34 g of silver nitrate in 200 ml of water for 10 minutes. Added to above solution. Next, a solution of 3.3 g of potassium iodide dissolved in 100 ml of water was added over 2 minutes. The pH of the silver iodobromide emulsion thus prepared was adjusted, and after sedimentation and removal of excess salt, the pH was adjusted to 6.0.
A total yield of 400 g of silver iodobromide emulsion was obtained. Emulsion Preparation Example 2 Preparation of benzotriazole silver emulsion Add 28 g of gelatin and 13.2 g of benzotriazole to water.
After stirring the solution while keeping it at 40° C., a solution of 17 g of silver nitrate dissolved in 100 ml of water was added to the solution over 2 minutes. Adjust the pH of this benzotriazole silver emulsion,
After sedimentation and removal of excess salt, the pH was adjusted to 6.0, yielding 400 g of benzotriazole silver emulsion. Emulsion Preparation Example 3 Preparation of benzotriazole silver emulsion containing photosensitive silver bromide 6.5 g of benzotriazole and 10 g of gelatin were added to water.
After stirring the solution while keeping it at 50°C, a solution of 8.5 g of silver nitrate dissolved in 100 ml 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 for 2 minutes, and the prepared emulsion was allowed to settle by adjusting the pH. After removing excess salt, the pH of the emulsion was adjusted.
Adjusted to 6.0. The yield was 200g. (Example of preparation of dye fixing material) Preparation of dye fixing material R-1 Poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride) is 1:1) 10g
100g 10% lime processed gelatin dissolved in 200ml water
mixed evenly. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 20 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) 4g urea (b) 8ml water (c) 10% polyvinyl alcohol (saponification degree 98%)
Weight% aqueous solution 12g (d) 5% aqueous solution of the following compound 2ml (e) 5% aqueous solution of sodium dodecylbenzenesulfonate 0.5 ml Photosensitive material preparation example 1 Preparation of photosensitive material E-1 Preparation of a dispersion of reducible dye-releasing agent 5 g of reducible dye-releasing agent IA-(9), Electron donor substance ED-(22) 4g, 2-ethyl-hexyl succinate sodium sulfonate 0.5g, tri-
20 ml of cyclohexanone was added to 10 g of cresyl phosphate (TCP) and dissolved by heating to about 60°C. After stirring and mixing this solution and 100 g of 10% gelatin solution, use a homogenizer for 10 minutes.
Dispersed at 10000RPM. 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) 25 g (b) Dispersion of reducible dye releasing agent DP-1 33 g (c) 10% ethanol solution of guanidine trichloroacetic acid 15 ml (d) Next 10 ml of a 2.5% aqueous solution of the compound shown in (e) N,N-dimethylsulfonamide 10% aqueous solution
At least 4 ml of (a) to (e) were mixed with 2 ml of water, 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. (f) 35 g of 10% gelatin aqueous solution (g) 6 ml of guanidine trichloroacetic acid 10% ethanol solution (h) 4 ml of 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate (i) Mix 55 ml of water, After coating to a wet film thickness of 25 μm, it was 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 10 seconds at 2000 lux using a tungsten bulb, and then uniformly heated for 30 seconds on a heat block heated to 130°C. 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.
The mixture was heated uniformly for 30 seconds on a heat block heated to 120°C. When the dye-fixing material was peeled off from the photosensitive material, a positive magenta color image was obtained on the dye-fixing material. The density of this positive image was measured using a Macbeth transmission densitometer (TD-504), and the maximum density for green light was 1.55 and the minimum density was 0.37. Moreover, the gradation of the sensitometric curve was a density difference of 1.06 for a 10 times the exposure amount difference in the straight line portion. The above results demonstrate 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 used in Photosensitive Material Preparation Example 1
Reducible dye releasing agent IB-(7) instead of IA-(9)
A photosensitive material E-2 was prepared in exactly the same manner as in Photosensitive Material Preparation Example 1, except that 5 g was used. Next, except that the dye transfer aid shown in Table 1 was used instead of urea used in dye fixing material preparation example 1,
Dye fixing materials R-2 to R-6 were prepared in exactly the same manner as dye fixing material R-1. Example 1 except that photosensitive material E-2 was used instead of photosensitive material E-1 used in Example 1, and dye fixing materials R-2 to R-6 were used instead of dye fixing material R-1. Exposure, heating, and
The density of the positive color image was also measured. The results are shown in Table-1.

[Table] The above results demonstrate that 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 obtained without supplying anything. It was done. In addition, dye fixing materials (R-5,
6), it was possible to obtain particularly sharp images with excellent surface gloss. Example 3 25g of silver iodobromide emulsion used in photosensitive material preparation example 1
Instead, 20 g of silver iodobromide emulsion and 10 g of silver benzotriazole (emulsion preparation example 2) were used, and reducible dye releasing agent -(20) was used instead of reducible dye releasing agent IA-(9). ), reducible dye-releasing agent IA-(7), or reducible dye-releasing agent-
Photosensitive materials E-3 to E-5 were prepared in exactly the same manner as in Photosensitive Material Preparation Example 1, except that 5 g of each quinone (18) was used. Exposure, heating, and density measurement of positive color images 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. . The results are shown in Table-2.

[Table] From the above results, even when using the reducible dye releasing agent shown in Table 2, by using a dye fixing material containing a hydrophilic thermal solvent, cyan and magenta can be improved even without supplying water at all. , it was demonstrated that a yellow positive dye image could be obtained. Example 4 The procedure was exactly the same as in Photosensitive Material Preparation Example 1, except that 25 g of silver benzotriazole containing silver bromide (Emulsion Preparation Example 3) was used instead of 25 g of the silver iodobromide emulsion used in Photosensitive Material Preparation Example 1. A photosensitive material E-6 was prepared. 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 in place of Photosensitive Material E-1 used in Example 1. The maximum density of the positive magenta color image on the dye-fixing material was 1.68, and the minimum density was 0.35. Example 5 Completely the same as Example 1 except that 0.4 g of 1-phenyl-4-methyl-4-oxymethyl-3-pyrazolidone was added as an electron transfer agent to the coating solution for the photosensitive material in Photosensitive Material Preparation Example 1. operated and processed. The density of the resulting magenta image was 1.60 at maximum and 0.29 at minimum, demonstrating that the addition of the electron transfer agent contributed to improving image quality. Example 6 The amount of guanidine trichloroacetic acid used in Photosensitive Material Preparation Example 1 was reduced to 1/2, and the reducible dye releasing agent IA-
In place of (9), 5 g of the quinone form of the reducible dye-releasing agent (17) was used, and in addition, the electron-donating substance ED-
4 g of electron donating substance ED-(1) instead of (22),
Photosensitive materials E-7 to E-9 were prepared in exactly the same manner as in Photosensitive Material Preparation Example 1, except that 4 g of ED-(13) or 4 g of ED-(23) was used. Further, dye fixing material R-7 was prepared in exactly the same manner as 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 placed in close contact with the dye-fixing material R-7 with their film surfaces facing each other on a heat block. 45 at 130℃
heated for 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 model (TD-504). The results are shown in Table-4.

[Table] 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.

Claims (1)

[Claims] 1 A positive silver halide photosensitive material having at least a photosensitive silver halide, a binder, an electron donor and/or an electron transfer agent, and a reducible dye releasing agent is placed on a support after imagewise exposure or after imagewise exposure. A dry method characterized in that the mobile dye formed in the unexposed area is moved under high temperature conditions in the presence of at least one kind of hydrophilic thermal solvent by heating at the same time, and is fixed to the dye fixing layer. Image forming method.