JPS6214145A - Positive image forming device - Google Patents

Abstract

PURPOSE:To form a good reversal image by subjecting a silver halide photosensitive material to image exposing then increasing the surface sensitivity of silver halide without using water then developing. CONSTITUTION:The silver halide photosensitive material having a silver halide emulsion layer contg. internal latent image type silver halide which is not preliminary subjected to fogging is preliminarily subjected to a stage for image exposing and thereafter the surface sensitivity of the silver halide is increased by using substantially no water and is then the photosensitive material is developed. The surface sensitivity of the silver halide is increased by resting the internal silver halide photosensitive material for a prescribed period in an active gaseous atmosphere of, for example, gaseous hydrogen, gaseous ammonia, sulfurous acid gas, gaseous hydrogen sulfide, etc.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for forming a positive image, and more specifically, the present invention relates to a method for forming a positive image. The present invention relates to a novel positive image forming method for obtaining a positive image by increasing the surface sensitivity of the silver halide without involving water. [Back of invention I! ] It is well known that positive photographic images can be formed directly using silver halide photosensitive materials without the need for intermediate processing steps or negative photographic images. Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. One type uses an emulsion containing pre-coupled silver halide, and utilizes solarization or the Burschel effect to eliminate fog nuclei (latent images) in exposed areas.
A developed erosive positive image is obtained by destroying the . The other type uses an emulsion containing internal latent image type silver halide that has not been coupled in advance, and performs surface development after image exposure and/or while performing fogging treatment to form a positive image. It's something you get. Here, the fogging treatment applied in the latter type is usually
A method of exposing the entire surface to light in a developer solution or a bath before development, or a method of using a fogging agent is employed. Also,
An emulsion containing internal latent image type silver halide refers to a silver halide emulsion which has photosensitive nuclei mainly inside silver halide grains and forms a latent image inside the grains upon exposure. This latter type of method is generally more sensitive than the former type of method and is suitable for applications requiring high sensitivity. A method for directly obtaining a positive image by imagewise exposing a photosensitive material using an emulsion containing internal latent image type silver halide and then subjecting it to full exposure or surface development in the presence of a fogging agent, and such method The photographic emulsion or light-sensitive material used is, for example, disclosed in U.S. Pat. Nos. 2,456,953 and 2,49
No. 7,875, No. 2,497,876, No. 2,49
No. 7,917, 2,507.15L@, 2,588
, No. 982, No. 2,563,785, No. 2,675,
No. 318, No. 3,227.552, No. 3,447,
No. 927, No. 3,511,662, British Patent No. 1,1
It is known as No. 51,363. Although it cannot be said that the details of the mechanism for forming direct positive images using emulsions containing internal latent image type silver halide have been clearly explained so far, for example, Mies and James [The As discussed in Theory of the Photographic Process, 4th edition, p. 190, it is possible to understand to some extent the process by which a positive image is formed by the desensitizing effect of an internal latent image. In other words, fog nuclei are selectively generated only on the surface of unexposed silver halide grains due to the surface desensitization effect caused by the so-called internal latent image created inside the silver halide grains by the first image exposure, and then normally By surface development of
It is thought that a photographic image is formed in the unexposed area by developing the fog nuclei. By the way, most of the above-mentioned known techniques attempt to improve photographic properties by improving silver halide emulsion manufacturing techniques, but improvements by processing processes are not well known. Also, U.S. Patent Nos. 4,124.3137 and 4,186
, No. 009 describes a photothermographic material that obtains a positive image through dry processing, but these publications also disclose that an emulsion containing internal latent image type silver halide is applied to a heat-developable photosensitive material. There is no suggestion as to how to directly form a positive image. As a result of extensive research into positive image formation using silver halide photosensitive materials, the present inventors have discovered that after image exposure, a silver halide photosensitive material having an emulsion containing internal latent image type silver halide contains substantially no water. The present inventors have discovered that by increasing the surface sensitivity of silver halide without the involvement of silver halide, fog nuclei can be selectively formed and positive images can be formed, and this has led to the present invention. [Object of the Invention] A first object of the present invention is to provide a novel positive image forming method that forms a good reversal image. A second object of the present invention is to provide a positive image forming method using a heat-developable photosensitive material that forms a good reversal image. [Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide photosensitive material having a silver halide emulsion layer containing internal latent image type silver halide that has not been coupled in advance, after the step of imagewise exposing it, substantially This was achieved by a positive image forming method comprising the steps of increasing the surface sensitivity of the silver halide without involving water, and then developing. [Specific Structure of the Invention] Regarding the internal latent image type silver halide whose surface is not coupled in advance to be used in the present invention, for example, U.S. Pat.
No. 592,250, No. 3,206,313, No. 3.3
No. 17,322, No. 3,511,662, No. 3,
No. 447,927, No. 3.761.266, No. 3,7
As described in No. 03,584 and No. 3.736.140, it is a silver halide whose internal sensitivity is higher than that of the surface of the silver halide grain. The method for preparing silver halide emulsions containing these internal latent image type silver halides is, for example, initially A9
A method in which a C1 grain is prepared and then bromide or a small amount of iodide is added to it to perform halide exchange, or a method in which a central core of chemically sensitized silver halide is converted into a non-chemically sensitized halogenated grain. Many methods are known, such as coating with silver or mixing a chemically sensitized coarse grain emulsion with a chemically sensitized or non-chemically sensitized fine grain emulsion and depositing a fine grain emulsion on the coarse grain emulsion. . Also, U.S. Patent Nos. 3,271, 157 and 3,447,927.
Silver halide emulsions having silver halide grains containing polyvalent metal ions as described in @ and US Pat. No. 3,531,291, or US Pat.
A silver halide emulsion in which the grain surface of silver halide grains containing a doping agent described in No. 6 is weakly chemically sensitized,
or silver halide emulsions comprising grains having a layered structure as described in JP-A-50-8524, JP-A-50-38525, and JP-A-53-2408;
These include silver halide emulsions described in No. 2-156614 and JP-A-55-127549. The silver halide emulsion containing internal latent image type silver halide used in the present invention (hereinafter referred to as internal latent image type silver halide emulsion) has a maximum density that can be achieved when developed with an "internal type" developer. It can be further defined by saying that the density is greater than the maximum density achieved when developed with a "surface-type" developer. The internal latent image type silver halide emulsion suitable for the present invention is produced by coating the silver halide emulsion on a transparent support and exposing it to light for a fixed time of 0.01 to 1 second, as described below as "internal type".
When the silver halide emulsion exposed in the same manner as above is developed in developer A at 20°C for 3 minutes, the maximum density measured by a normal photographic density measuring method is determined by the following "surface type" carrier solution B: has a density at least five times greater than the maximum density obtained when developed at 20° C. for 4 minutes. [Developer A Cohydroquinone 15g Metol 15g Anhydrous Sodium Sulfite 50g Potassium Bromide
10 g sodium hydroxide
25a Sodium thiosulfate
Add 20g water 11
2 [Developer B Cop-Hydroxyphenylglycine 109 Sodium Carbonate Add 100g water
12 A feature of the present invention is that an internal latent image type silver halide emulsion whose surface is not previously coupled as described above is subjected to imagewise exposure, thereby increasing the surface sensitivity of the silver halide without substantially involving water. The objective is to form a positive image. The internal latent image type silver halide used in the present invention is preferably in the range of 0.001 g/f to 100 g/f, more preferably 0.05111 g/f to 50 g/f in terms of silver.
It is in the range of Q/f. The internal latent image type silver halide used in the present invention includes any halogenated silver halide such as silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide. I can give you silver. The grain size of the above silver halide is such that the average grain size is 0.
．． 001 μm to 2 μm is preferable, more preferably 0
．． 01 μm to 1 μm. Two or more types of silver halides having different sizes and/or halogen compositions may be used in combination. In the present invention, the average grain size refers to the particle diameter of 9 for silver halide grains that are spherical or approximately spherical, the principal diameter for cubic grains, and the projected area for silver halide grains other than spherical or cubic. The diameter of each area circle was expressed as an average based on the projected area, which was taken as the particle size. It is something. Preferred internal latent image type silver halide grains used in the present invention are conversion type silver halide grains? The particles have a core/shell structure in which the core is further coated with silver halide as a shell, and is disclosed in JP-A-55-127.
No. 549 discloses this in detail. The conversion type silver halide core in the internal latent image type silver halide grains used in the present invention means that at least some silver salt grains having a higher solubility in water than silver bromide are formed, and then at least one of the grains is These are silver halide grains made by converting a portion of silver bromide or silver iodobromide. Usually, it is easily prepared by mixing an aqueous silver nitrate solution and an aqueous chloride solution in the presence of a protective colloid such as gelatin, and then adding an aqueous bromide solution to the resulting silver chloride emulsion. The conversion type silver halide core grains in the present invention preferably contain at least 80 mol % of silver bromide, and may contain up to 10 mol % of silver iodide. Particularly preferred is a conversion type silver halide core containing at least 90 mol% silver bromide and 5 mol% or less (including 0 mol%) silver iodide, with the remaining halide being silver chloride. The core/shell structured silver halide grains used in the present invention have a structure made by depositing silver halide on the surface of the conversion type silver halide core grains to form a silver halide shell. It is a particle. The silver halide of the shell may be composed of any one of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Furthermore, the thickness of the shell is such that the silver halide content of the shell is 30% based on the total silver halide constituting the core/shell.
A mole % to 70 mole % is sufficient. If the silver halide content of the shell is less than 30 mol%, storage stability at high temperatures tends to be poor and the minimum concentration tends to increase;
If it exceeds 0 mol%, the maximum concentration will decrease. Further, a highly preferable internal latent image type silver halide emulsion used in the present invention is, for example, US Pat. No. 3,206,31
No. 6, No. 3,317,322, No. 3,367.7
No. 78, No. 3,447,927, No. 3,531,
No. 291, No. 3,271,157 and No. '3,
Examples include metal ion doped emulsions described in the specifications of No. 761,276, and core/shell type emulsions in which the interior of the grains is chemically sensitized. Internal latent image type silver halide emulsions useful in the present invention include:
It is an emulsion containing silver halide grains that occlude foreign metal ions or metal compounds inside the silver halide grains. Different metal ions are ions other than silver ions. These foreign metal ions or metal compounds occluded inside the silver halide grains can include sulfur, sulfur compounds, metallic iridium, gold, platinum, and the like. Different metal ions or metal compounds can be occluded inside silver halide grains by forming silver halide grains in the presence of these ions or compounds. For example, a foreign metal ion or a metal compound is first deposited on a silver halide grain that will eventually become a core, and then silver halide that is to become a shell is deposited around the outer periphery of the silver halide grain. Accordingly, a different metal ion or a metal compound can be occluded inside the silver halide grains. The emulsion containing internal latent image type silver halide grains used in the present invention refers to silver halide grains in which latent images are mainly formed inside the silver halide grains and most of the photosensitive nuclei are inside the grains. The emulsion containing silver halide in this case includes, for example, silver bromide, silver chloride, silver chlorobromide,
This includes silver iodobromide, silver chloroiodobromide, and the like. However, among these, internal latent image type silver halide emulsions which are particularly useful in the present invention are those in which the silver halide is primarily silver bromide, and preferably comprises at least 50 mole percent silver bromide. It is an emulsion containing silver particles. The internal latent image type silver halide emulsion of the present invention is prepared by first preparing R silver halide grains that will eventually become cores, and then performing gold or noble metal sensitization, sulfur sensitization, and so on by methods known in the art. reduction sensitization at the same time, or a combination of two of these sensitization methods, such as gold sensitization and sulfur sensitization, or one of these sensitization methods, such as sulfur sensitization. A so-called core/shell emulsion is preferred, in which the silver halide grains are chemically sensitized using a chemical sensitizer, and then silver halide, which is to become a shell, is deposited on the outer periphery of the silver halide grains. As mentioned above, any silver halide composition can be used for the core/shell emulsion used in the present invention. Further, the silver halide composition of the core portion and the silver halide composition of the shell portion may be the same or different. In a preferred embodiment of the silver halide composition of the core part and shell part of the present invention, the core part contains 0 to 4 mol% Ag.
I content is silver iodobromide, and the shell part is 0.5
Silver iodobromide with an AQI content of ~8 mol%. It is preferred that the AgI content m of the shell portion is greater than the AOI content of the core portion. For example, the ACl + content of the shell part is higher than the Ag content of the core part.
It is preferable that the content is 1 mol % or more. One of the most preferred embodiments is a silver iodobromide core/shell emulsion in which the core portion is a pure silver bromide emulsion and the shell portion has an AgI content of 2 to 6 mol%. Furthermore, the thickness of the shell is such that the silver halide content of the shell is 30% based on the total silver halide constituting the core/shell.
Preferably, it is from mol% to 95 mol%. If the silver halide content of the shell is less than 30 mol %, the minimum density tends to increase, while if it exceeds 95 mol %, the maximum density decreases. The internal latent image type silver halide grains used in the present invention are produced by I) A! By appropriately controlling +, particles of various crystal forms can be produced. For example, grains having a cubic, octahedral, or dodecahedral crystal shape can be produced, and in the present invention, there are no particular limitations on the crystal habit of the silver halide grains. Next, a process for increasing the surface sensitivity of silver halide without substantially involving water will be described. An increase in the surface sensitivity of silver halide means that the surface sensitivity after the process has increased compared to the surface sensitivity of the silver halide before the process, and the degree of sensitization is The emulsion has a silver coating j of 3.5 to 4.5 (J
/f compared to the applied one and the unapplied one,
It is preferable that the sensitized one is at least 0.10 larger. [Exposure conditions] Exposure for 171,000 seconds

[Developer formulation] p-hydroxyphenylglycine 10 (1 carbonate
Add 100g of sodium water
1 [Processing temperature, time] Developed at 20°C for 4 minutes [Sensitivity display method] Exposure required to give a temperature of fog density + 0.1
Photographic sensitivity of negative images expressed as the common logarithm of the reciprocal of the amount of light
. Silver halide surfaces of the present invention substantially without the involvement of water
In the process of increasing sensitivity, seeds are used as a sensitizing means.
Various methods can be used. For example, hydrogen gas, ammonia gas, sulfur dioxide gas, sulfide
The photosensitive material of the present invention must be placed in an atmosphere of active gas such as hydrogen gas.
Increases the surface sensitivity of silver halide by allowing it to stand for a certain amount of time.
can be done. Additionally, ultrasonic waves are applied to the photosensitive material.
Sensitization can also be increased by others,
Increases silver halide surface sensitivity with virtually no water involvement
Any method that can be used to make people feel
You can stay there. In the present invention, [J without substantially involving water] means halogen.
In the step of increasing the surface sensitivity of silver oxide,
This means that the material does not contain substantially any water. If water is included, the effect of the present invention will only be weakened.
This results in fogging, which is not desirable in practice. However, the original
It is permissible to contain water to the extent that it does not impair the light effect. good
Preferably, in the process of increasing the surface sensitivity of silver halide.
Moisture content of the photosensitive material before storage is determined as follows:
It is 10% by weight or less of the mold content. Preferable steps for increasing surface sensitivity of silver halide of the present invention
A preferred embodiment is hydrogen sensitization using hydrogen gas. General
Regarding the hydrogen sensitization method of silver halide photosensitive materials,
The embankment was proposed by J.A. ABCock and others.
“Photographic Science and Engineering
Alling” (Photographic 5cien
ce and Engineering) Volume 13 54
Pages, Vol. 15, p. 75, Vol. 19, pp. 49-55.
and pages 211-214, ゛°Legal of Photo
Graphic Science” (Journal o
f Photographic Science) 2nd
Volume 4, pages 19-24, U.S. Patent No. 3,891,446;
No. 3,984,249, Special Publication No. 50-35810
It is described in JP-A No. 54-121728, etc.
, in the present invention, these techniques can be referred to.
can. Next, hydrogen sensitization treatment will be explained in detail. The silver halide photographic light-sensitive material is first depressurized and then exposed to hydrogen gas.
Hydrogen sensitization treatment is performed under a gas atmosphere. Depressurization is carried out in the hydrogen gas treatment vessel and the silver halide photographic emulsion layer.
An operation whose purpose is to remove oxygen and moisture from
, usually for 1 minute at a vacuum level of 10-2 Torr or less.
or more. Furthermore, in order to fully achieve the purpose of this operation, the container after depressurization
A hydrogen gas atmosphere is introduced into the
May be repeated several times. This operation and the container used are as follows:
With a pressure gauge attached to each end of the vibrator or tube
Just use a container. Regarding the method of treatment with hydrogen gas, refer to the above-mentioned literature or special
by the same method as described in the patent publication or specification.
Therefore, it is done. In the present invention, "hydrogen gas atmosphere" means substantially oxygen gas atmosphere.
and does not contain water vapor, and all 1 is hydrogen gas or a part of it
to an inert gas such as nitrogen, neon, helium, or argon.
It means something more profane. The pressure of such hydrogen gas atmosphere is based on the hydrogen gas partial pressure.
Types and processing of silver halide photographic materials that should be processed according to
You can set it freely by comprehensively considering the relationship with temperature, time, etc.
can be done. A practically preferable range is, for example, when the pressure is
10-3~10 atm, temperature 20~80℃, time 30
seconds to 16 hours. In addition to the sensitization treatment using hydrogen gas as described above, the present invention
, ammonia gas, sulfur dioxide gas, hydrogen sulfide gas
Regarding sensitization treatment using active gas such as hydrogen sensitization,
It can be used in the same way as the treatment. A preferred embodiment of the invention is that the surface is precoupled.
The internal latent image type silver halide emulsion is not chemically sensitized.
A core/shell emulsion having a core of
After imagewise exposing the photosensitive material, the photosensitive material is placed in a hydrogen gas atmosphere.
Increase the surface sensitivity by placing it under
By performing a development process suitable for the photosensitive material, positive images can be created.
Form an image. In the present invention, a light fogging process is carried out prior to development processing.
can be provided. In addition, there is a possibility that the photosensitive material or developer may contain
Chemical fogging is performed by containing a fogging agent.
You can also do that. The optical fogging process can be performed by exposing the entire surface to light.
I can do that. Full-surface exposure is imagewise exposure of the photosensitive material of the present invention.
The photosensitive material may be made substantially free of water, e.g.
After performing the hydrogen sensitization treatment, the photosensitive material is treated with a developer.
or after immersion or moistening in other aqueous solutions;
The entire surface is exposed uniformly in a dry state without being immersed in water.
This is done by The light source used here is
, any light within the wavelength range to which the photographic light-sensitive material is sensitive.
Do not expose the device to high-intensity light such as flash light for a short period of time.
You can also expose it to weak light for a long time. Ma
In addition, the total exposure time depends on the photosensitive material, processing conditions, and the method used.
Depending on the type of light source used, etc., the final positive image may not be obtained.
It can be varied widely to suit your needs. A wide range of fogging agents can be used in the present invention.
This fogging agent can be used to
It only needs to be present during processing, for example, as a support for photographic materials.
(especially in the silver halide emulsion layer)
(preferably), a developer, or a developer prior to the development process.
It may also be included in the processing solution. Also, the amount used is
Preferred additions that can be varied over a wide range depending on the purpose
As a group, when added to a silver halide emulsion layer,
1 to 1500 mg per mole of silver halide, particularly preferred
The amount is 10 to 1000 mg. In addition, processing of developer, etc.
The preferred addition level when adding to the liquid is 0.01 to 5M.
12, particularly preferably from 0.05 to 19/2. As the fogging agent used in the present invention, for example, US Pat.
No. 2,563.785 and No. 2,588,982.
Dorazine listed in the specification or US special
Hydrazi described in Patent No. 3,227,552
or hydrazone compound: U.S. Patent No. 3,615.6
No. 15, No. 3,718,470, No. 3,719,
494, 3.734.738 and 3.7
Heterocyclic quaternary nitrogen described in each specification of No. 59,901
Salt compounds; also U.S. Pat. No. 4,030,925
The acylhydrazinophenylthioureas mentioned above are mentioned.
Ru. Also, these fogging agents can be used in combination.
Wear. For example, research disclosure (Research Disclosure) N
o, 15162 uses a non-adsorption type fogging agent and an adsorption type fogging agent.
It has been described that it can be used in combination with a yellowtail agent. Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine [1! , 4-methylphenylhydride
Radine hydrochloride, 1-formyl-2-(4-methylphenylphenyl)
) hydrazine, 1-acetyl-2-phenylhydrazide
1-acetyl-2-(4-acetamidophenyl)
Hydrazine, 1-methylsulfonyl-2-phenyl
Hydrazine, 1-benzoyl-2-phenylhydrazine
, 1-methylsulfonyl-2-(3-phenylsulfonyl)
(amidophenyl) hydrazine, formaldehyde
Hydrazine compounds such as phenylhydrazine; 3-(2-
formylethyl)-2-methylbenzothiazolium bro
Mide, 3-(2-formylethyl)-2-propylbene
ndzothiazolium bromide, 3-(2-acetyl ethyl
)-2-benzylbenzoselenazolium bromide,
3-(2-acetylethyl-2-benzyl-5-phene)
Nyl-benzoxacilium bromide, 2-methyl-
3-[3-(phenylhydrazono)propyl]benzothi
Azolium bromide, 2-methyl-3-[3-(p-
t-Rylhydrazono)propyl 1-benzothiazoliumb
Lomide, 2-methyl-3-[3-(p-sulfophe)
Nylhydrazono)propyl] benzothiazolium broma
ido, 2-methyl-3-[3-(p-sulfophenyl
hydrazono)pentylbenzothiazolium iodite
, 1,2-hydro-3-methyl-4-phenylpyrido [
2,1-b]benzothiazolium bromide, 1.2
-dihydro-3-methyl-4-phenylpyrido [2,1
-b]-]5-phenylbenzoxacilium broma
4.4'-ethylenebis(1,2-dihydro-3-
Methylpyrido[2,1-b]benzothiazolium broma
id), 1,2-dihydro-3-methyl-4-phenyl
Pyrido[2,1-b]benzoselenazolium bromide
N-W1 of de etc! I! Quaternary cycloammonium salt; 5
-C1-ethylnaphtho(1,2-b)thiazoline-2-
ylideneethylidene]-1-(2-phenylcarbazoy
) methyl-3-(4-sul)7moylphenyl)-2
-Thiohydantoin, 5-<3-ethyl-2-penzothi
azolinylidene)-3-[4-<2-formylhydra
dino)phenyl 10-danine, 1-[4-(2-phor)
milhydrazinone phenyl]-3-phenylthiourea,
1゜3-bis[4-(2-formylhydrazino)fe
Examples include nilkothiourea. The following margin describes the development process of the silver halide photosensitive material used in the present invention.
In this case, any development processing method can be adopted.
. One of the preferred embodiments of the development step of the present invention is a surface developer
This is a surface development process using This surface development process
Processing means processing with a developer substantially free of silver halide solvents.
It means to understand. The developer used in the development process of the photographic light-sensitive material used in the present invention.
Commonly used developers that can be used in image solutions include
Conventional silver halide developers, such as hydroquinone
Polyhydroxybenzenes, aminophenols, 3-
Pyrazolidones, ascorbic acid and its derivatives, Redac
Tons, phenylene diamines, etc. or mixtures thereof.
included. Specifically, hydroquinone, aminophenol, N-methane
Thylaminophenol, 1-phenyl-3-virazolide
1-phenyl-4,4-dimethyl-3-pyrazolide
1-phenyl-4-methyl-4-hydroxymethyl
-3-pyrazolidone, ascorbic acid, N,N-diethyl
Le-p-phenylenediamine, diethylamino-o-1
-Luidine, 4-amino-3-methyl-N-ethyl-N
-(β-methanesulfonamidoethyl)aniline, 4
-amino-3-methyl-N-ethyl-N-(β-hydro
xyethyl)aniline, etc. These developers
is included in the emulsion in advance and immersed in a high pH aqueous solution.
It is also possible to make it act on silver halide inside.
. The developer used in the present invention also has specific fogging properties.
may contain inhibitors and development inhibitors, or
These developer additives can be optionally added to the constituent layers of photographic materials.
It is also possible to incorporate it into Usually useful anti-fog
Agents include benzotriazoles, such as 5-methylbenzene.
Zotriazole, benzimidazoles, benzothiazo
benzoxazoles, 1-phenyl-5-mer
Heterocyclic thiones such as lucapotetrazole, aromatic
and aliphatic mercapto compounds. Also,
The developer contains a development accelerator, such as polyalkylene oxa.
Id derivatives and 4th I! ! Contains ammonium chloride etc.
You can also do it. Internal latent image type silver halide emulsion used in the present invention (hereinafter referred to as the present invention)
The silver halide emulsion of the invention) comprises silver halide grains.
Unnecessary soluble salts may be removed to terminate the growth of
Alternatively, it may be left as is. remove the salts
In this case, the research disk Ojit-(Resea
rch D 1 closure >Described in No. 17643
This can be done based on the method of The silver halide emulsion of the present invention is widely used in the photographic industry for sensitized color.
Light is transmitted to the desired wavelength range using a known dye.
It can be scientifically sensitized. Sensitizing dyes may be used alone, but
You may use two or more types in combination. With sensitizing dye
dyes that do not themselves have a spectral sensitizing effect, or visible
A compound that does not substantially absorb light and is a compound that enhances sensitizing dyes.
A supersensitizer that increases the sensitization effect may be included in the emulsion.
. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dye, complex merocyanine dye, Holopolar
- Cyanine dyes, hemicyanine dyes, styryl dyes and
and hemioxanol dyes are used. Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. These pigments
is commonly used in cyanine dyes as a basic heterocyclic nucleus.
Any of the following nuclei can be applied. i.e. vilorin nucleus
, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxa
Zole nucleus, thiazole nucleus, selenazole nucleus, imidazole
ole nucleus, tetrazole nucleus, pyridine nucleus, and these nuclei.
Nuclei of fused alicyclic hydrocarbon rings: and these nuclei have aromatic
A nucleus in which aromatic hydrocarbon rings are fused, that is, an indolenine nucleus,
Benzindolenine nucleus, indole nucleus, penzoxoza
Naphthothiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, naphthothiazole nucleus, naphthothiazole nucleus,
Phthothiazole nucleus, benzoselenazole nucleus, benzimide
These include dazole nuclei and quinoline nuclei. These cores are charcoal
May be substituted on elementary atoms. Keto defeated by merocyanine dyes or complex merocyanine dyes
Pyrazolin-5-one as a nucleus with methylene structure
nucleus, thiohydantoin nucleus, 2-thioxazolidine-2
．． 4-dione nucleus, thiazolidine-2,4-dione nucleus, 0
- 5- to 6-membered heteromorphs such as danin nucleus and thiobarbic acid nucleus
Ring nuclei can be applied. Sensitizing colors used in useful blue-sensitive silver halide emulsion layers
For example, West German patent 929.08ON, US patent
No. 2,231,658, No. 2,493,748, No. 2,493,748, No.
No. 2,503, 776, No. 2,519,001, No. 2,519,001, No. 2,519,001, No.
No. 2,912,329, No. 3,656,959, No. 2,912,329, No. 3,656,959, No.
No. 3,672,897, No. 3,694,217,
No. 4,025,349, No. 4,046,572, English
National Patent No. 1,242.588, Special Publication No. 14030/1973
4. List the items described in No. 52-24844, etc.
be able to. Also used in green-sensitive silver halide emulsions.
Examples of useful sensitizing dyes include those described in US Pat.
No. 39,201, No. 2.072,908, No. 2.7
No. 39,149, No. 2,945,763, British Patent
Cyanine dyes such as those described in No. 505,979 etc.
, merocyanine dyes or complex cyanine dyes are representative examples.
It can be mentioned as something similar. In addition, red-sensitivity
Useful sensitizing dyes used in silver halide emulsions include
, for example, U.S. Patent Nos. 2,269,234 and 2,27
No. 0,378, No. 2,442,710, No. 2,45
4,629, 2,776.280, etc.
cyanine dyes, merocyanine dyes or composite dyes such as
Anine dyes can be cited as a representative example.
Ru. Furthermore, U.S. Pat. No. 2,213,995, 2,4
93,748N, No. 2,519,001, West German Patent 9
Cyanine dyes such as those described in No. 29.080, etc.
Green photosensitive merocyanine dye or complex cyanine dye
Advantageously used in silver halide emulsions or red-sensitive halogen emulsions.
I can be there. These sensitizing dyes may be used alone, but they may be used in combination.
A combination may also be used. Especially the combination of sensitizing dyes
, often used for the purpose of supersensitization. A typical example is
, Special Publication No. 43-4932, No. 43-4933,
No. 43-4936, No. 44-32753, No. 45-2
No. 5831, No. 45-26747, No. 46-1162
No. 7, No. 46-18107, No. 47-8741,
No. 47-11114, No. 47-25319, No. 4γ
-37443, 4g-28293, 4g-38
No. 406, No. 48-38407, No. 48-38408
No. 48-41203, No. 48-41204, No. 48-41203, No. 48-41204, No.
No. 49-6207, No. 50-40662M, No. 53-1
2375M, No. 54-34535, No. 55-1569
No., JP-A-50-33220, JP-A No. 50-33828
, No. 50-38526, No. 51-707727, No. 51-707727, No. 50-38526, No. 51-707727, No.
No. 51-115820, No. 51-135528,
No. 51-151527, No. 52-23931, No. 52-23931, No. 52-23931, No. 52-23931, No.
No. 52-51932, No. 52-104916, No. 52
-104917, 52-109925, 52-
No. 110618, No. 54-80418, No. 56-25
No. 728, No. 57-1483, No. 58-10753
, No. 58-91445, No. 58-153926, No. 58-153926, No. 58-91445, No. 58-153926, No.
No. 59-114533, No. 59-116645, No. 5
9-1166474, U.S. Patent No. 2.688,545
, No. 2,977.229, No. 3,397,060,
No. 3,506,443, No. 3,578,447, No. 3,578,447, No.
No. 3,672,898, No. 3,679.428, No. 3
, No. 769,301, No. 3,814,609, No. 3
．． No. 837,862. Used with sensitizing dyes, which themselves have spectral sensitizing effects.
Pigments that do not have this or substances that do not substantially absorb visible light
Examples of substances that exhibit strong color sensitization include aromatic
Organic acid formaldehyde condensates (e.g., U.S. Pat.
, 437,510), cadmium salts,
Zaindene compounds, amino acids substituted with nitrogen-containing heterocyclic groups
Stilbene compounds (e.g., U.S. Pat. No. 2,933,3
No. 90, those described in No. 3,635.721), etc.
be. U.S. Patent No. 3,615.613, U.S. Patent No. 3,615
, No. 641, No. 3,617,295, No. 3.635
, 721 are particularly useful. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
layer, and other hydrophilic colloid layers are coated with a binder (or
A hardening agent that cross-links (protective colloid) molecules and increases film strength.
Hardening can be achieved by using one or more types.
Ru. The hardener is so strong that it is not necessary to add it to the processing solution.
The amount of photosensitive material that can be hardened can be added at a time, but
It is also possible to add a hardening agent to the processing solution. As a hardening agent, aldehyde type, aziridine type (e.g.
, P8 Report, 19,921, U.S. Patent No. 2.950
, No. 197, No. 2,964,404, No. 2,98
Specifications of No. 3,611 and No. 3,271,175,
JP 46-40898, JP 50-91315
)-, isoxazole-based (e.g.
For example, as described in U.S. Pat. No. 331.609
), epoxy systems (e.g., U.S. Pat. No. 3,047,39
No. 4, West German Patent No. 1,085,663, British Patent No. 1
, 033,518, Japanese Patent Publication No. 48-3549
5), vinyl sulfone type (e.g.
, PB Report 19,920, West German Patent No. 1,100,
No. 942, No. 2,337,412, No. 2.545,7
No. 22, No. 2,635,548, No. 2,742,
No. 308, No. 2,749,260, British Patent Nos. 1 and 2
No. 51,091, Patent Application No. 1983-54236, No. 48-
110996, U.S. Patent No. 3,539.644,
3.490,911), a.
Kryloyl type (for example, Japanese Patent Application No. 48-27949, U.S.
What is stated in each specification of National Patent No. 3.640.720
), carbodiimide systems (e.g., U.S. Pat. No. 2,938
．． 892@, No. 4,043,818, No. 4.06L4
Specifications of No. 99, Japanese Patent Publication No. 4B-38715, Japanese Patent Publication No. 4B-38715,
(as described in the specification of Application No. 15095/1983), Tria
Gin series (for example, West German Patent No. 2,410,973,
No. 2,553,915, U.S. Patent No. 3,325,287
Each of the light m layers of the No.
), polymeric types (e.g. British Patent No. 822,061
No. 3,623.878, U.S. Patent No. 3,396.
No. 029, 8mei Jall of No. 3,2213.234,
Special Publication No. 18578, No. 18579, No. 47-
48896), other maleimi
De-based, acetylene-based, methanesulfonic acid ester-based, (
N-methylol type hardeners alone or in combination
Can be used. As a useful combination technique, for example, West Germany
Patent No. 2,447,587, Patent No. 2,505,746
, No. 2,514,245, U.S. Patent No. 4,047,9
57@, No. 3,832,181, No. 3,840,37
Details of No. 0, JP-A No. 48-43319, JP-A No. 50-
No. 63062, No. 52-127329, Special Publication No. 1973-
Examples include combinations described in each publication of No. 32364.
. The emulsion layer of the light-sensitive material used in the present invention is subjected to color development treatment.
In the process, aromatic primary amine developers (e.g. p-fluoride)
phenylenediamine derivatives, aminophenol derivatives, etc.
Coupling reaction with the oxidized form of ) to form a pigment
Dye-forming couplers are used. The dye-forming coupler is
Absorbs light in the emulsion layer's sensitive spectrum for each emulsion layer
It is usually selected to form a pigment that
, a yellow dye-forming coupler in the blue-sensitive emulsion layer, and a green-sensitive emulsion layer.
The red-sensitive emulsion layer contains a magenta dye-forming coupler, and the red-sensitive emulsion layer contains a magenta dye-forming coupler.
A cyan dye-forming coupler is used in the layer. However
However, depending on the purpose, it can be used in different ways than the above combinations.
A silver halide color photographic material may also be produced. These dye-forming couplers have a ballast group in their molecules.
has a group having 8 or more carbon atoms that makes the coupler non-diffusive
This is desirable. Moreover, these dye-forming couplers have one molecule
4 silver ions are reduced to form the pigment
Even with the required 4-equivalence, two silver ions are reduced
Either of the 2 and B properties is acceptable. pigment formation
The coupler has the ability to react by coupling with the oxidized form of the developing agent.
Development accelerator, bleach accelerator, developer, silver halide solvent
, toning agent, hardening agent, fogging agent, antifogging agent, chemical sensitization
photographically useful agents such as agents, spectral sensitizers, and desensitizers;
Can contain compounds that release fragments
. These dye-forming couplers have color-correcting effects.
Colored couplers or development inhibitors used during development
DIR that improves image sharpness and image graininess
A coupler may also be used in combination. At this time, DIR coupler
The dye formed from the coupler is used in the same emulsion layer.
is the same family as the dye formed from the dye-forming coupler.
However, if the color is not noticeable, it may be different.
It may also be one that forms different types of pigments. DIR coupler
In place of this, an oxidized form of a developing agent can be used with or in combination with the coupler.
At the same time, a colorless compound is produced by a coupling reaction with
DIR compounds that release development inhibitors may also be used. The DIR couplers and DIR compounds used include
One in which the inhibitor is directly bound to the coupling position, and the other in which the inhibitor is bound directly to the coupling position.
It is bonded to the coupling position via a divalent group, and the cup
Intramolecular nucleophilic reaction within the group separated by ring reaction,
Inhibitor is released by intramolecular electron transfer reaction, etc.
Combined timing DIR coupler and timing
(referred to as DIR compounds). Also, inhibitors
Withdrawal - post-diffusion and not-so-diffusion
Depending on the purpose, things can be used alone or in combination.
Wear. Oxidized product of aromatic primary amine developer and coupling
A colorless coupler that undergoes a mixing reaction but does not form a dye is used as a dye.
It can also be used in combination with forming couplers. The yellow dye-forming coupler used in the present invention is
, known acylacetanilide couplers are preferably used.
I can be there. Among these, benzoylacetoacetate
Nilide and pivaloylacetanilide compounds are advantageous
It is. Specific examples of yellow couplers that can be used are given in British Patent No.
No. 1,077.874, Special Publication No. 45-40757, Special
Kaisho No. 47-1037, Kaisho 47-26133, Kaisho 48
-94432, 50-87650, 51-36
No. 31, No. 52-115219, No. 54-99433
No. 54-133329, No. 56-30127,
U.S. Patent No. 2,875,057, U.S. Patent No. 3,253,9
No. 24, No. 3,265,506, No. 3,408,
No. 194, No. 3,551,155, effect 3.551,1
No. 56, No. 3,664.841, No. 3,725.0
No. 72, No. 3.730.722, No. 3.891, 4
No. 45, No. 3,900.483, No. 3,929,
No. 484, No. 3,933,500, No. 3,973,9
No. 68, No. 3,990,896, No. 4,012,25
No. 9, No. 4,022,620, No. 4,029.508
No. 4,057,432, No. 4,106,94
No. 2, No. 4, +33.958, No. 4,269,9
No. 36, No. 4,286,053, No. 4,304,8
No. 45, No. 4,314,023, No. 4,336,32
No. 7, No. 4,356,258, No. 4,386.155
No. 4,401.752, etc.
. The magenta dye-forming coupler used in the present invention is
, known 5-virazolone couplers, pyrazolobenzi
Midazole couplers, pyrazolotriazole couplers
- Preferably use open-chain acylacetonitrile couplers.
I can be there. A specific example of a magenta coupler that can be advantageously used is disclosed in the patent application filed in 1973.
No. 8-164882, No. 58-167326, No. 58
-206321, 58-214863, 58
-217339, No. 59-24653, Special Publication No. 1977
-6031, 40-6035, 45-4075
No. 7, No. 47-27411, No. 49-37854,
JP-A No. 50-13041, JP-A No. 51-26541, JP-A No. 51-26541,
No. 51-37646, No. 51-105820, No. 52
-42121, 53-123129, 53-
No. 125835, No. 53-129035, No. 54-
No. 48540, No. 56-29236, No. 56-756
No. 48, No. 57-17950, No. 57-35858
, No. 57-146251, No. 59-99437,
British [El patent 1? , 252,418, U.S. Pat.
．． 600.7. ! No. 18, No. 3,005,712, No. 18, No. 3,005,712, No.
No. 3,062,653, No. 3,127,269, No. 3
, No. 214,437, No. 3,253,924, No. 3,
311.476, 3,419,391, 3
, No. 519.429, No. 3.558, 319, No. 3
, No. 582, 322, No. 3,615,506, No. 3
, No. 658,544, No. 3,705,896, No. 3,
No. 725,067, No. 3,758,309, No. 3,8
No. 23,156, No. 3,834.908, No. 3,8
No. 91,445, No. 3,907,571, No. 3.9
No. 26,631, No. 3,928,044, No. 3,
No. 935,015, No. 3,960,571, No. 4.0
No. 76.533, No. 4,133,686, No. 4,23
No. 7,217, No. 4,241,168, No. 4,264
．． No. 723, No. 4,301,235, No. 4,3
10,623 etc. 1! It is what was done. The cyan dye-forming couplers used in the present invention include:
Prefers known naphthol couplers and phenol couplers.
It can be used correctly. Cyancap that can be used advantageously
Specific examples of
, No. 543,040, Japanese Patent Publication No. 48-36894, Japanese Patent Publication
No. 48-59838, No. 50-137137, No. 5
No. 1-146828, Zhou No. 53-105226, same
No. 54-115230, No. 56-29235, No. 5
6-156-1 (No. 513126833, No. 5
No. 7-133650, No. 57-155538, No. 57
-204545, 5g-118643, 59-
No. 31953, No. 59-31954, No. 59-596
No. 56, No. 59-124341, No. 59-16695
No. 6, U.S. Patent No. 2,369,929, U.S. Patent No. 2,423
, No. 730, No. 2,434,272, No. 2,474,
No. 293, No. 2,698,794, No. 2,772,
No. 162, No. 2,801,171, No. 2,895.
No. 826, No. 3,253,924, No. 3,311
, No. 476, No. 3.458, 315, No. 3,476
．． 563@, No. 3,591,383, No. 3,737
, No. 316, No. 3,758,308, No. 3,767.
No. 411, No. 3,790,384, No. 3,880,6
No. 61, No. 3,926.634, No. 4,004,9
No. 29, No. 4,009,035, No. 4.012, 2
No. 58, No. 4,052,212, No. 4,124,
No. 396, No. 4,134,766, No. 4,138,2
No. 58, No. 4,146,396, No. 4,149,88
No. 6, No. 4,178,183, No. 4,205.990
No. 4,254,212, No. 4,264,72
No. 2, No. 4.288,532, Mukai 4,296.19
No. 9, No. 4,296,200, No. 4,299,91
No. 4, No. 4,333,999, No. 4,334,011
No. 4,386.155, No. 4,401,7
No. 52, No. 4,427.767, etc.
It is. Hydrophilic layers, intermediate layers, etc. of photosensitive materials used in the present invention
The sexual colloid layer is caused by the photosensitive material becoming charged due to friction, etc.
Prevents fogging caused by discharge, and prevents image deterioration caused by UV light.
It may contain an ultraviolet absorber to prevent UV rays. As the ultraviolet absorber used in the present invention, benzophene
Non-compounds (e.g. JP-A No. 46-2784, U.S. patent
No. 3,215,530, No. 3,698,907
), butadiene compounds (e.g., U.S. Pat.
, 045, 229), 4-thiazolidone
compounds (e.g., U.S. Pat. No. 3,314,194;
3.352,681), substituted with an aryl group
benzotriazole compounds (e.g.,
No. 6-10466, No. 41-1687, No. 42-26
No. 187, No. 44-29620, No. 48-41572
No., JP-A-54-95233, JP-A No. 57-142975
No. 3,253,921, U.S. Patent No. 3.533,
No. 794, No. 3,754,919, No. 3,794
, No. 493, 4,009,038%, 4,220.
No. 711, No. 4,323,633, Research Diss.
Closure (Research[) 1sclosure
re) described in No. 22519), benzioki
didole compounds (e.g., U.S. Patent No. 3.700.45)
No. 5) cinnamic acid ester compounds (e.g.
U.S. Patent No. 3,705,805, U.S. Patent No. 3.707.37
No. 5, described in JP-A No. 52-49029).
can be done. Zarani, U.S. Patent No. 3,499,76
No. 2, and those described in JP-A No. 54-48535 are also used.
be able to. UV-absorbing couplers (e.g. α-
naphthol-based cyan dye-forming couplers) and ultraviolet absorbing
Acidible polymers (e.g., JP-A-58-111942)
, No. 178351, No. 181041, No. 59-19
No. 945, those described in Publication No. 23344), etc.
I can be there. These UV/UV absorbers are
It may be mordanted. Magenta dye formation by formalin during storage of photosensitive materials
Used in the present invention to prevent deterioration of couplers etc.
Formalin scavenger can be used for photosensitive materials.
can. Halogen in photosensitive materials using the silver halide emulsion of the present invention
Sensitive to silver oxide emulsion layer and/or other hydrophilic colloid layer
Reduction of gloss of materials, improvement of stiffness, mutual bonding of photosensitive materials
A matting agent can be added to prevent sticking. Sliding friction of photosensitive materials using the silver halide emulsion of the present invention
A lubricant can be added to reduce the The photosensitive material using the silver halide emulsion of the present invention has antistatic properties.
Antistatic agents can be added to prevent static electricity. The antistatic agent prevents static electricity on the side of the support that is not laminated with the emulsion.
It may be used in the emulsion layer and/or the support.
Protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated
May be used for. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
layer and/or other hydrophilic colloid layers may include coatability improvements,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, photographic properties
For the purpose of improving properties (promotion of development, hardening, sensitization, etc.),
A variety of surfactants can be used. Examples of anionic surfactants include alkyl carboxyl
phosphate, alkyl sulfonate, alkylbenzene
sulfonate, alkylnaphthalene sulfone M salt, a
alkyl sulfates, alkyl phosphates, N
-Acyl-N-furkyltaurines, sulfosuccinates
Stelles, sulfoalkyl polyoxyethylene alkyl
Phenyl ethers, polyoxyethylene alkyl phosphorus
Carboxy groups, sulfo groups, such as acid esters, etc.
Acidic groups such as phospho groups, sulfate ester groups, phosphate ester groups, etc.
Those containing are preferred. Examples of amphoteric surfactants include amino acids, amino acids,
alkyl sulfonic acids, aminoalkyl sulfates or phosphoric acids
Stelles, alkyl betaines, amine oxides, etc.
preferable. Examples of cationic surfactants include alkyl amines.
salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary anhydrides such as pyridinium and imidazolium
monium salts, and phosphorus containing aliphatic or heterocycles.
Preferred are nium or sulfonium salts. Examples of nonionic surfactants include saponin (steel
(roid), alkylene oxide derivatives such as poly
Ethylene glycol, polyethylene glycol/polyp
Ropylene glycol condensate, polyethylene glycol
alkyl ethers or polyethylene glycol alkyl
Ruaryl ethers, polyethylene glycol esters
polyethylene glycol sorbitan esters,
Polyalkylene glycol alkylamine or amide
, silicone polyethylene oxide adducts
Glycidol derivatives (e.g. alkenyl succinic acid polyglycerides)
υceride, alkylphenol polyglyceride), polyvalent
Alcohol fatty acid esters, sugar alkyl esters
etc. are preferred. Used in photosensitive materials using the silver halide emulsion of the present invention.
The support may be an α-olefin polymer (e.g. polyester).
tyrene, polypropylene, ethylene/butene copolymer), etc.
Flexible reflective support such as laminated paper or synthetic paper, acetic acid
Cellulose, cellulose nitrate, polystyrene, polychloride
Vinyl, botaethylene terephthalate, polycarbonate
Fibers made of semi-synthetic or synthetic polymers such as polyester, polyamide, etc.
lums and flexible supports with reflective layers on these films.
Includes bodies, glass, metals, ceramics, etc. Coating a photographic material using the silver halide emulsion of the present invention
In this case, a binder may be used to improve the coating properties.
stomach. Also, for example, hardening agents, which have quick reactivity, can be used in advance.
When added to the coating solution, it may cause gelation before coating.
For materials, apply using a static mixer etc.
It is preferable to mix immediately beforehand. Other embodiments of the present invention include the sensor used in the present invention.
The optical material is a heat-developable photosensitive material and includes a thermal imaging process.
It is. Hereinafter, the case where the present invention is applied to a heat-developable photosensitive material will be explained.
Explain in detail. Heat-developable photosensitive materials are well known in the art, and are heat-developable.
Regarding photosensitive materials and their processes, U.S. Patent No. 3,15
No. 2,904, No. 3,301,678, No. 3,392
,020@, No. 3,457,075, British Patent 1
, No. 131, 108, 1,167.777M and Lisa
Church Disclosure No. 17029 (
(1978). Heat-developable photosensitive materials contain photosensitive silver halide, a binder, and
It consists of a composition containing a reducing agent as an essential component.
After image exposure, the temperature is usually 80°C or higher, preferably 100°C or higher.
An image is obtained by heating the top. Also, further
By including an organic silver salt in the composition of the photosensitive material,
Images with higher maximum density can be obtained. A heat-developable photosensitive material (hereinafter referred to as a heat-developable photosensitive material) which is one embodiment of the present invention
(referred to as a photosensitive material) has at least the above-mentioned surface on the support.
Uncoupled internal latent image type silver halide, suitable for thermal development
Therefore, organic silver salt and/or silver halide are reduced to silver.
During exposure, a silver image is created in the unexposed area due to chemical involvement in this reaction.
Both contain a dye-donating substance that stops or releases the dye.
The heat developable material has a silver halide emulsion layer that is
Pigments produced or released and unreacted pigments
The donor substance coexists and a clear dye image is obtained.
undesirable for Therefore, when the present invention is applied to thermal development 15 material,
The dye that is fixed or released imagewise by heat development is
, is preferably a diffusible dye, and the diffusible dye is
Excellent photographic properties are obtained by transferring the dye to the receiving layer.
A clear dye image can be obtained. In the present invention, at least the dye-providing substance, the surface of which is
Contains an uncoupled internal latent image type silver halide emulsion
The photosensitive layer and the color to which the generated or released dye is transferred
The element-receiving layer may be formed on the same support, or may be formed on a separate support.
It can also be formed on a support. The dye-receiving layer and photosensitive layer can also be peeled off. For example, after image exposure, the internal latent image type silver halide surface Jl
After the I-sensitization process is completed, heat development is performed to add silver to the unexposed areas.
Colors generated or released along with the image are transferred from the photosensitive layer.
Diffuse and transfer to the elementary image-receiving layer, then dye-receiving layer or photosensitive layer
can be torn off. In addition, there are photosensitive materials in which a photosensitive layer is coated on a support, and a dye-receiving material.
The layers are formed separately from the image-receiving material coated on the support.
In some cases, after image exposure on a photosensitive material, an internal latent image type halo is applied.
Surface sensitization treatment with silver germide, then heat development and heating
Due to the action of
After forming or releasing a diffusible dye, the image receiving material is
The dye produced or released in the photosensitive layer
can be transferred to the receptor layer. In addition, after exposing only the photosensitive material, internal latent image type halogen
The surface layer of silver oxide is sensitized, and then the image-receiving material is overlaid.
After that, heat development may be performed. Furthermore, only the light-sensitive material is exposed imagewise, and then the image-receiving material is exposed.
The dye is diffused and transferred to the dye-receiving layer by overlapping and heat development.
You can move it. Explain quality. As a dye-donating substance, a photosensitive halide is used.
Silver halides and/or organic silver salts used as necessary
involved in a reduction reaction and the diffusive color as a function of that reaction
Any substance that can form or release an element is sufficient, and the reaction
Depending on the form, negative-acting dye donors act in a positive function
quality (i.e., when negative-working silver halide is used)
(forming moth pigment images) and positive type acting on negative functions.
dye-donor (i.e. negative-working silver halide)
(forms a positive dye image when the dye is present). Negative dye-donor substances are further classified as Fukishita
. The dye-providing substance of each of the releasing type compound and forming type compound will be further explained. Examples of the reducing dye-releasing compound include those represented by general formula (1).
Included are the compounds shown. General formula (1) % formula % In the formula, Car represents photosensitive silver halide and/or as necessary.
During the reduction of organic silver salts used in
It is a reducing substrate (so-called carrier) that releases Dy
e is a diffusible dye residue. Specific examples of the above-mentioned reducible dye-releasing compounds include JP-A-Sho
No. 57-179840, No. 58-116537, No. 5
No. 9-60434, No. 59-65839, No. 59-7
No. 1046, No. 59-87450, No. 59-8873
No. 0, No. 59-123837, No. 59-165054
No. 59-165054, etc.
Examples include the following compounds. Below are examples of dye-providing substances in the margin.
Examples include compounds represented by: General formula (z) In the formula, A1 and A2 are hydrogen atoms and hydroxy groups, respectively.
or represents an amino group, and Dye is represented by general formula (1)
It is synonymous with DVe. Specific examples of the above compounds are given in JP-A-59
-'124,329. As a coupled dye-releasing compound, the general formula (U) is
Examples include compounds represented by: General formula ('))) % formula % In the formula, CP+ is a diffusible dye that reacts with the intensifying product of the reducing agent.
organic groups (so-called coupler residues) capable of releasing
], J is a divalent bonding group, and is an intensified form of a reducing agent.
The reaction 1) cleaves the bond between Cpl and J. nl is
Represents 0 or 1, Dye is defined by general formula (1)
It is synonymous with thing. Also, CP+ releases coupling dye.
Substitution with various ballast groups to make type compounds non-diffusible
It is preferable that the ballast group is
Depending on the form of the photosensitive material used, the number of carbon atoms is 8 or more (more
(preferably 12 or more) organic groups, sulfo groups, carboxyl groups,
Hydrophilic groups such as boxy groups, or 8 or more (more preferably
(12 or more) carbon atoms, sulfo groups, carboxy groups, etc.
It is a group having both hydrophilic groups. Another particularly preferred ballast group is a polymer chain.
can be done. Specific examples of the compound represented by the above general formula (3) are:
, JP-A-57-186,744, JP-A No. 57-12459
No. 6, No. 57-160,698, No. 59-174゜
For example, the following compounds may be mentioned. Exemplary dye-donor substance ■ OCR. ■ As a coupling dye-forming compound, the general formula (shown by
General formula (4) (% formula %) In the formula, C20 reacts with the intensified form of the reducing agent (coupling reaction).
organic groups (response) that can form diffusible dyes (
so-called coupler residue], X represents a divalent bonding group.
Q represents a ballast group 0 The color formed as a coupler residue represented by CR2
The molecular weight is preferably 700 or less for the sake of elemental diffusivity.
, preferably 500 or less. In addition, the ballast group is the ballast defined by general formula (3).
The same ballast group as the group is preferred, especially 8 or more (more preferably 8 or more).
Preferably 12 or more carbon atoms, sulfo group, carboxyl
A group having a hydrophilic group such as a
Rimmer chains are more preferred. Coupling dye-forming compound with this polymer chain and
is derived from a monomer represented by general formula (9).
Preferred are polymers having repeating units. General formula (5) % formula %) In the formula, CpzX is the same as defined in general formula (4)
l), Y is an alkylene group, arylene group or aralkyl group
Represents a lene group, Z represents a divalent organic group, and L represents an ethyl group.
Represents a group having an ethylenically unsaturated group or an ethylenically unsaturated group.
Was. Coupling dyes represented by general formulas (4) and (S)
Specific examples of forming compounds include JP-A-59-124゜3
No. 39, No. 59-181,345, Patent Application No. 58-10
No. 9.293, No. 59-179,657, No. 59-1
No. 81.604, No. 59-184506, No. 59-1
It is described in each specification etc. of No. 82.507, for example:
The following compounds may be mentioned□. Exemplary dye-providing substance ■ C1aHs Polymer ■ ClOcC0OH oC)b 0 x: 60% by weight y: 401i% C0NHCHsCH2CHCOOHCOOC4H9 Above
In general formulas (3), (4) and (5), Cpl or
further details the coupler residues defined in CF2.
Then, a group represented by the following general formula is preferable. General formula (ran) General formula (7) general formula ('
X) General formula (9) General formula (10)
General formula (11) General formula (1z)
General formula (General formula)
General formula (In formula 1, R+, R2, R9 and R4 are each
Re hydrogen! child, haloken atom, alkyl group, cycloalkyl
group, aryl group, acyl group, purkyloxycarbonyl group
group, aryloxycarbonyl group, alkylsulfony group
group, arylsulfonyl group, carbamoyl group, °sulfonyl group,
famoyl group, acyloxy group, amine group, alkoxy
group, aryloxy group, cyano group, ureido group, alkyl group
ruthio group, brylthio group, carboxy group, sulfo group or
represents a heterocyclic residue, which further includes water @ group, carboxyl group,
Oxy group, sulfo group, alkoxy group, cyano group, nitro group
, alkyl group, aryl group, aryloxy group, acyl
Oxy group, acyl group, sulfamoyl group, carbamoyl
may be substituted with a group, imide group, /・rogen R group, etc.
stomach. These substituents are Cp! and select according to the purpose of Cpt.
As mentioned above, in <CPs, one of the # substituents is a rose
It is preferable that it is a strike group, and in Cpz, it is not formed.
The molecular weight is 700 or less to increase the diffusibility of the dye.
The substituents are preferably selected to be 500 or less.
It is preferable that As a positive dye-donating substance, for example, the following general formula (C
G) There is an oxidizing hydrogen releasing compound represented by the general formula
(1b) In the formula, Wl is quinone ant (having a substituent in this loam)
represents the collection of atoms necessary to form
RT; represents an alkyl group or a hydrogen atom. ] or
-8O2-, r represents 0 or 1, ])ye
is the same as that defined by the general formula (1).
Specific examples of compounds are given in JP-A-59-166.954 and JP-A-59-166.954.
- It is stated in the specifications such as No. 154,445, etc.
There are the following compounds. Exemplary dye-donating substances■. ■ OC'H3 Another positive dye-donor substance is expressed by the following general formula (17).
When fermented, the compound released is represented by the compound represented by
There are compounds that make you lose your powers of death. General formula (l'7) In the formula, W2 is benzene*< which may have a substituted group on the ring.
R5 represents the group of atoms necessary to form
, E, and Dye are general formulas (synonymous with those defined in mind).
Ru. A specific example of this compound is JP-A-59-124,329
No. 59-154,445, etc.
For example, there are the following compounds. Exemplary dye-donating substance CH3 Still another positive dye-donating substance is represented by the following general formula (
Examples include compounds represented by I. General formula (1g) In the above formula, W2, R5, and Dye are in general formula (17).
It is synonymous with 9 things that are defined as 0 and the specifics of this compound.
An example is described in JP-A-59-154,445, etc.
, for example, there are the following compounds.
7), Diffusible dye represented by Dye in (18)
The residues will be described in further detail. As a residue of diffusible dye
The molecular weight is preferably 800 or less due to the diffusivity of the dye.
It is preferably 600 or less, and an azo dye,
Azomethine dye, anthraquinone dye, naphthoquinone color
element, styryl dye, nitro dye, quinoline dye, carbo
Examples include residues such as nyl dyes and phthalocyanine dyes. These dye residues can create multiple colors during thermal development or transfer.
It may also be in a temporary shortwave form. In addition, these pigment residues
The group is used for the purpose of increasing the light resistance of images, for example,
Described in No. 48765 and No. 59-124337
A chelatable dye residue is also a preferred form.
. These dye-providing substances may be used alone or in combination of two or more.
May be used above. The amount used is not limited, and it provides pigmentation.
The type of substance, whether it is used alone or in combination of two or more, or
The photographic structure 1i of the photosensitive material of the present invention has 12 layers as a single layer or
The decision can be made depending on whether there are two or more layers, but for example,
The amount used is 1■2 per V) 0.005g ~So
p, preferably 0.1 g to 10 g can be used
. The dye-providing substance used in the present invention is used in heat-developable color photosensitive materials.
The method of incorporating it into the photographic constituent layer is arbitrary. For example, low
Boiling point solvents (methanol, ethanol, ethyl acetate, etc.) or
or high boiling point solvents (dibutyl phthalate, dioctyl phthalate)
ester, tricresyl phosphate, etc.).
Long sonic dispersion or alkaline aqueous solution (e.g.
After dissolving in 10% sodium hydroxide aqueous solution, etc.), mineral acid
(For example, hydrochloric acid or nitric acid, etc.)
or an aqueous solution of a suitable polymer (e.g. gelatin,
(polyvinyl butyral, polyvinyl lolidone, etc.)
It can be used after being dispersed using a ball mill.
Wear. Preferred implementation of the present invention in the following margins! ! ! Mr. Kapura in advance
organic silver salt along with latent image type silver halide.
However, as the Yuyu silver salt, it was not exposed to light.
In the presence of silver halide, at a temperature of 80'C or higher, preferably
When heated to over 100℃, it reacts with the reducing agent and forms a silver image.
As a comparative fishing spot for light that produces
No. 4, No. 44-26582, No. 45-18416,
No. 45-12700, No. 45-22185 and special
No. 49-52626, No. 52-31728, No. 5
No. 2-13731, No. 52-141222, No. 53-
No. 36224, No. 53-3622, U.S. Patent i
No. 3,330,633, No. 4,168.980, etc.
Silver salts of aliphatic carboxylic acids listed in the specifications of
For example, Laurin Ml! ! , silver myristate, palmitic acid
Silver, silver stearate, silver arachidonate, silver behenate, etc.
Also silver aromatic carboxylates, such as silver benzoate, phthalate
silver, and silver salts with imino groups, such as benzotria
Sol silver, saccharin silver, phthalazinone ° silver, phthalai
Compounds with mercapto or thione groups, such as midsilver
silver salts, such as 2-mercaptobenzoxazole silver,
Silver mercaptooxadiazole, mercaptobenzothia
Sol silver, 2-mercaptobenzimidazole silver, 3-
mercapto-phenyl-1,2,4-triazole silver,
In addition, 4-hydroxy-6-methyl-1,3
, 3a, 7-chitrazaindene silver, 5-methyl-7-h
DoOxy-1゜2.3,4.6-pentazaindene silver, etc.
can be given. t RD 16966, (Fj 16907, UK EE
lSpec rF No. 1,590.956, 'same number 1,590,
Silver compounds such as those described in No. 957 Mei I8I may also be used.
I can do it. Among them, for example, the silver salt of silver benzotriazole
Silver salts having imino groups such as benzotriazo
Examples of silver salts include methylbenzotriazole.
Le silver-like alkyl I! benzotriazole silver, e.g.
Eh, silver bromo-benzotriazole, chlorobenzot
Halogen-substituted benzotriazoles such as silver lyazole
silver, such as 5-7 cetamidobenzotriazole silver.
Unamide-substituted benzotriazole silver, also patented by Aida
l! No. 1,590,956, Zhou l 1,590,95
7@Compounds described in each Akizuna Fu, such as N-[6-rioo
-4-N (3,5-dichloro-4-hydroxyphenylene
) imino-1-oxo-5-methyl-2,5-Schiff O
Hexadien-2-yl 1-5-carbamoylbenzot
Riazole silver salt, 2-benzotriazol-5-ylua
Zo-4-methoxy-1-naphthol silver salt, 1-benzoto
Riazol-5-ylazo-2-naphthol silver salt, N-
Benzotriazol-5-yl-4-(4-dimethyla
Examples include minophenylazo)benzamide silver salt. Also, nitrobenzotris represented by the following general formula (1q)
Azoles and benzene represented by the following general formula (2o)
Zotriazoles can advantageously be used. In the following formulas, R11 represents a nitro group, R1U and R/3
may be the same or different, each with a halogen atom (e.g.
(for example, chlorine, bromine, iodine), droxy group, sulfo group
or its salts (e.g. sodium salts, potassium salts, ammonia salts)
carboxy group or its salt (e.g.
Sodium salt, potassium salt, ammonium salt λ, nitro
group, cyano group, or each group may have a substituent.
Rubamoyl group, sulfamoyl group, alkyl group (e.g.
methyl group, ethyl group, propyl group), alkoxy group (e.g.
(e.g. methoxy group, ethoxy group), aryl group (e.g.
phenyl group) or amino group, and the intestine is 0 to 2, n
represents 0 or 1. Furthermore, if the carbamoyl group is
As a substituent (for example, methyl group, ethyl group, acetyl group)
! M substituent of sulfamoyl group can be mentioned.
For example, methyl group, ethyl group, acetyl group, etc.
Examples of substituents for alkyl groups include
Carboxy group, ethoxycarbonyl! ! ! etc., ant
Examples of one substituent of the metal group include a sulfo group, a nitro group, etc.
As a substituent for the alkoxy group, for example, carboxy
substituents for groups, ethoxycarbonyl groups, and amine groups
For example, acetyl group, methanesulfonyl group, hydrogen
Each of the drooxy groups can be mentioned. The compound represented by the general formula (I9) has at least one
Silver salt of benzotriazole derivative with two nido DI
The following compounds are given as specific examples:
Can be done. For example, 4-nitrobenzotriazole silver, 5-nitrobenzotriazole
silver triazole, 5-nitro-6-chlorobenzot
Riazole silver, 5-nitro-6-methylbenzotriazo
silver, 5-nido-0-6-methylbenzotriazole silver
, 5-nidro-phenylbenzotriazole silver, 4
-Hydroxy-5-nitrobenzotriazole silver, 4-
Hydroxy-7-nitrobenzotriazole silver, 4-hydroxy
Droxy-5,7-dinitrobenzotriazole silver, 4
-Hydroxy-5-nitro-6-chlorobenzotriazo
silver, 4-human Oxy-5-nitro-6-methylben
Zotriazole silver, 4-sulfo-6-nitrobenzotri
Azole silver, 4-carboxy-6-di-O-benzotria
Sol silver, 5--carboxy-6-nitrobenzotria
Sol silver, 4-carbamoyl-6-nitrobenzotria
Sol silver, 4-sulfamoyl-6-nitrobenzotri
Azole silver, 5-carboxymethyl-6-nitrobenzo
Triazole silver, 5-hydroxycarbonylmethoxy-
6-nitrobenzotriazole silver, 5-nitro-7-di
Atsubenzotriazole silver, 5-amino-6-nitrobe
silver nizotriazole, 5-nitro-7-(p-nido
benzotriazole silver, 5,7-dinitro-6
-Methylbenzotriazole silver, 5,7-sinitro〇
-benzotriazole silver, 5,7-dinitro-6
- May include silver methoxybenzotriazole, etc.
Wear. General formula <20) In the formula, R/+ is a hydroxy group, a sulfo group, or an atom thereof.
(e.g. sodium salts, potassium salts, ammonium salts)
, carboxy group or its salt (e.g. sodium salt
, potassium salt, ammonium salt), which may have substituents.
a carbamoyl group and a sulfur group which may have a substituent
represents a moyl group, and Rtg is a halogen atom (e.g. chlorine
, bromine, iodine), hydroxy group, sulfo group or their
salts (e.g. sodium salts, potassium salts, ammonium salts)
), carboxy group or in situ (e.g. sodium salt
, potassium salt, ammonium salt), nitro group, cyan group
, or an alkyl group that may each have a substituent (e.g.
For example, methyl group, ethyl group, propyl group), aryl group (
For example, tuunyl group) alkoxy group (for example, methoxy group,
ethoxy group) or an amino group, p is 1 or
2, Q represents an integer from O to 2. In addition, as the M group of the carbamoyl group in R and +,
Examples include methyl group, ethyl group, acetyl MW.
11fJ of the sulfamoyl group! ! , l and
For example, methyl groups, ethyl groups, acetyl groups, etc.
can be given. Furthermore, the alkyl group in R
As the 1Mk base, for example, carboxy group,
As a substituent for an aryl group, for example, a carbonyl group, etc.
Ruho group, nido 0 group, etc. are used as M substituents of alkoxy group.
, for example, carboxy group, ethoxycarbonyl MW, or
and M substituent of amino group, for example, acetyl group meta
sulfonyl group, hydroxy 1j! etc., respectively.
Can be done. A specific example of the organic silver salt represented by the general formula (2o) is
The following compounds can be mentioned. For example, 4-hydroxybenzotriazole silver, 15-
Droxybenzotriazole silver, 4-sulfobenzotri
Azole silver, 5-sulfobenzotriazole silver, benzo
Sodium triazole silver-4-sulfonate, benzoto
Sodium lyazole silver-5-sulfonate, benzotri
Azole silver-4-potassium sulfonate, benzotriazo
potassium silver-5-sulfonate, benzotriazole
Ammonium silver-4-sulfonate, pensitriazo 15
-ammonium silver-5-sulfonate, 4-carboxylate
Cybenzotriazole silver, 5-carboxybenzotriazole
Sol silver, benzotriazole silver-4-carboxylic acid sodium salt
potassium benzotriazole silver-5-carboxylate
potassium benzotriazole silver-4-carboxylate,
Pensitriazolyl silver-5-carvone potassium
, benzotriazole silver-4-carboxylic acid ammonium
, ammonium benzotriazole silver-5-carboxylate
, 5-carbamoylbenzotriazole silver, 4-sulfur
Amoylbenzotriazole silver, 5-carboxy-6-
Hydroxybenzotriazole silver, 5-hydroxy-7
- Sulfobenzotriazole silver. 4-Hydroxy-5-sulfobenzotriazole silver, 4
-Hydroxy-7-sulfobenzotri7zole silver, 5.
6-dicarboxybenzotriazole silver, 4,6-schich
Droxypenzotriazole silver, 4-hydroxy-5-
Silver benzotriazole, 4-hydroxy-5-methane
Tylbenzotriazole silver, 4-hydroxy-5-meth
Xybenzotriazole silver, 4-hydroxy-5-ditho
silver lopenzotrizole, 4-'hydroxy-5-sia
Nobenzotriazole silver, 4-hydroxy-5-amino
Benzotriazole silver, 4-hydroxy-5-7 setoa
Midobenzotriazole silver, 4-hydroxy-5-ben
Zensulfonamide benzotriazole silver, 4-hydro
xy-5-hydroxycarbonylmethoxybenzotria
Sol silver, 4-hydroxy-5-ethoxycarbonylmetal
Toxybenzotriazole silver, 4-hydroxy-5-ka
Ruboxymethylbenzotriazole silver, 4- and droxy
-5-ethoxycarbonylmethylbenzotriazole silver
, 4-hydroxy-5-7I-benzotriazole silver
, 4-hydroxy-5-1p-nitrophenyl)benzo
Triazole silver, 4-human 0x-5-(p-sulfof
phenyl) benzotriazole silver, 4-sulfo-5-chloro
Rubenzotriazole silver, 4-sulfo-5-methylben
Zotriazole silver, 4-sulfo-5-methoxybenzot
Riazole silver, 4-sulfo-5-cyanobenzotriazo
silver, 4-sulfo-5-7 minobenzotriazole silver
, 4-sulfo-5-acetamidobenzotriazole silver
, 4-sulfo-5-benzenesulfonamide benzotri
Azole silver, 4-sulfo-5-hydroxycarbonylmetal
Toxybenzotriazole silver, 4-sulfo-5-ethoxy
Cycarbonylmethoxybenzotriazole silver, 4-hydro
Roxy-5-carboxybenzotriazole silver, 4-su
Rufo-5-carboxymethylbenzotriazole silver, 4
-sulfo-5-ethoxyluponylmethylbenzotri
Azole silver, 4-sulfo-5-phenylbenzotriazo
silver, 4-sulfo-5-(E)-nitrophenyl) base
silver, 4-sulfo-5-(p-sulfof)
phenyl) benzotriazole silver, 4-sulfo-5-meth
xy-6-diO-benzotriazole silver, 4-sulfo-
5-chloro-6-carboxybenzotriazole silver, 4
-carboxy-5-chlorobenzotriazole silver, 4-
Carboxy-5-methylbenzotriazole silver, 4-carboxy-5-methylbenzotriazole
Ruboxy-5-nitropenzotriazole silver, 4-cal
Boxy-5-aminobenzotriazole silver, 4-carbo
xy-5-methoxybenzotriazole silver, 4-carbo
xy-5-acetamidobenzotriazole silver, 4-carboxylic
Ruboxy-5-ethoxycarbonylmethoxybenzotri
Azole silver, 4-carboxy-5-carboxymethyl base
silver zotriazole, 4-carboxy-5-phenylbene
silver, 4-carboxy-5-(p-nito
Lophenyl) pencitriazole silver, 4-carboxy-
5-Methyl-7-sulfobenzotriazole silver etc.
can be given. Even when used alone, these compounds
Two or more types may be used in combination. The organic silver salt that can be preferably used in combination with the present invention can be prepared by a known method.
4, and the organic silver salt is I! Use the separated items in an appropriate way
It may be used by dispersing it in a binder, or
The silver salt was prepared in a suitable binder and then removed without isolation.
It may be used as is. The amount of organic silver salt used is 0 per mole of silver halide.
．． 01 mol to 500 mol is preferable, more preferably 0
．． The amount is 1 mol to 100 mol. The average particle size of the organic silver salt is about 10 μm to about 0.01 μm.
m is preferable, more preferable 11. < is about 5 μm to about 0.1
It is μm. Internal latent image type silver halide and/or used in combination as necessary
is oxidized by organic silver salts and reacts with dye-donating substances.
and a reducing agent that has the ability to form or release a dye.
is a color that forms a dye image by oxidative camping.
- A developing agent is useful. Examples of such reducing agents include
For example, 4-N, N described in JP-A-56-146133
-Dialkylphenylsulfamic acids, also N, N
-diethyl-p-phenylenediamine, N-phenyl-
such as N-isopropyl-〇-phenylenediamine, etc.
N,N-dialkyl-p-phenylenediamines, etc.
The so-called
A p-phenylenediamine color developing agent is used.
. In addition, for example, 4-amino-2,6-diku00
Phenol, 4-amino-2-methylphenol sulfate
4-amino-2,6-dichlorophenol
Aminophenols such as Doroku O Ride are also preferably used.
It will be done. Furthermore, 2,67 di-O-4-4-substituted sulfonamide
Phenolic reducing agents such as enol, 4-amino-naphtho
derivatives and 4-substituted sulfonamide naphthol derivatives
naphthol-based reducing agent, such as U.S. Patent No. 2,895,8
Aminohuman Oxypyrazole derivatives described in 25M
, amino as described in U.S. Pat. No. 2,892,714.
Pyrazoline derivatives, also Research Disclosure t-
N 0019412fl and the same No. 19415 (June 1980 issue)
Radin derivatives are useful. Even if these reducing agents are used alone, the reducing agents described in fjJ
You may use two or more types in combination, including. The reducing agent used in the present invention is used in a certain degree range.
Ru. A useful reducing agent concentration cycle is internal i-image silver halide 1 mo.
preferably from 0.01 mol to 1500 mol, more preferably
Preferably it is 0.1 mol to 200 mol. In addition to the reducing agents mentioned above, the following reducing agents may also be used for auxiliary development.
It can also be used as an agent. Useful auxiliary agents include hydroquinone, t-butyl
Hydroquinone, 2,5-dimethylhydroquinone, etc.
7 Lucyltecols, pyrogallols, chlorohydroquinone,
Halogen-substituted hydroquinone such as dichlorohydroquinone
Flukoxy-substituted hydrogens such as methoxyhydroquinone,
Polyhydroquinones, methylhydroxynaphthalene, etc.
There is oxybenzene In form. In addition, methyl galley
G., ascorbic acid, ascorbic acid derivatives, N. N
'-di(2-ethoxyethyl)hydroxylamine
Hydroxylamines such as 1-phenyl-3-pyrazo
Lydone and 4-methyl-4-hydroxymethyl-1-phene
Pyrazolidones such as nyl-3-pyrazolidone, reductants
Useful examples include esters, hydroxytetronic acids, and hydroxytetronic acids. The auxiliary developer used in the present invention is used within a certain concentration range.
can be done. The useful concentration range is 1 molar silver halide.
The range is preferably 0.01 mol to 1500 mol per mol.
, more preferably 0.1 mol to 200
Suitable binders include hydrophilic or hydrophobic binders.
The reader can be used arbitrarily depending on the purpose. For example,
Proteins such as latin, gelatin derivatives, cellulose derivatives
body, polysaccharides such as dextran, arabic
increase the dimensional stability of natural substances such as aluminum, and photographic materials.
A latex-like vinyl compound and the following synthesis
Contains polymer. The preferred synthetic polymer is the US
Patent No. 3,142,586, Patent No. 3,193.386
No. 3,062,674@, No. 3,220,84
No. 4, No. 3,287,289, No. 3,411,9
11@, which have been modified by 2 in each specification. Useful polymers include alkyl acrylates, meth
Acrylate, acrylic acid, sulfoalkyl acrylate
Or there are water-insoluble polymers made of methacrylate.
can be lost. A suitable polymeric material is polyvinylbutylene.
Ral, polyacrylamide, cellulose acetate
thyrate, cellulose acetate propionate, poly
Methyl methacrylate, polyvinyl vinylone, poly
Tyrene, ethyl cellulose, polyvinyl chloride, salt
Plain rubber, polyisobutylene, butadiene styrene copo
Limer, vinyl chloride-vinyl acetate copolymer
-, vinyl acetate - vinyl chloride - maleic acid
copolymers with, polyvinyl alcohol, polyvinyl acetate
cellulose, benzyl cellulose, cellulose acetate, cellulose
Propionate, cellulose acetate phthalate are listed.
can be lost. Among these polymers, especially polyvinyl butyl
Ral, polyvinyl acetate, ethylcellulose, polymethylene
methacrylate, cellulose acetate butyrate
preferable. If necessary, two or more types may be used in combination. In the present invention, the binder is a hydrophilic binder.
is preferred. "Hydrophilic" here means water or water and organic
Soluble in a mixed solution with a solvent (a solvent that can be arbitrarily mixed with water)
An example of a hydrophilic binder is
Gelatin, gelatin derivatives, cellulose derivatives, dex
Polysaccharides such as Tolan, gum arabic, etc.
Polygonylacetate as a natural substance and effective polymer
Tar (preferably the degree of acetalization is 20% or less, e.g.
(polyvinyl butyral), polyacrylamide, poly
Vinyl lolidon, ethylcellulose, polyvinylalcohol
Coal (preferably one with a saponification degree of 75% or more) @
Can be mentioned. These can be used in combination of two or more types as necessary.
You may. The amount of binder is determined by the internal latent image type halogen per each photosensitive layer.
It is preferably 0.01 to 100 times, more preferably 0.01 to 100 times as much as silver oxide.
or 0.05 to 50 times, and per 112 of the support.
0.2~sog (total heat development of binder of each layer)
The imagewise distribution of the thermally transferable dye is obtained by
The imagewise distribution of color formed from a given substance onto the image receiving member
For example, methanol, acetonitrile, dimethyl
Conversion using Fj&m agents such as chillformamide and water
Copying, thermal transfer using a hot solvent, sublimation of the dye itself, etc.
Various transfer methods can be used, such as thermally mobile transfer.
However, if the photosensitive material contains a thermal solvent
The dye can be transferred by simply heating the image receiving member in close contact with it.
can be set. The image receiving member used in the present invention can be released or released by heat development.
It only needs to have the function of receiving the formed pigment, and the pigment can be expanded.
Mordants used in scatter transfer photosensitive materials and JP-A-57-2
The glass transition temperature described in 072504 etc. is 40'C.
Made of heat-resistant organic polymer material above 250℃
It is preferable. Variant examples of the mordants include nitrogen-containing secondary and tertiary mordants.
Mins, nitrogen-containing complexes! A-ring compounds, these quaternary cations
compound, U.S. Pat. No. 2,548,564, 2. t
No. 84,430, No. 3,148,061, No. 3,75
Vinylpyridine polymers disclosed in No. 6,814
and Vinylpyridinium Cationic Polymer, U.S. Pat.
No. 2,675,316
Polymers containing mino groups, U.S. Pat. No. 2,882,156
Aminoguanidine derivatives disclosed in JP-A No. 1983
Covalently reactive polymers described in No. 4-137333
-, U.S. Patent No. 3,625,694, 3,85
No. 9,096, British Patent &! No. 1,277.453,
Gelatin disclosed in No. 2,011,012
Crosslinkable Mordant, U.S. Pat. No. 3,958,995
No. 2,721,852, No. 2.798,06
Aqueous sol type mordant disclosed in No. 3, JP-A-1988-1
61228, a water-insoluble mordant disclosed in US Pat.
Patent No. 3,788,855, West German patent application (018)
No. 2,843,320, JP-A-53-30328@,
52-155528@, 53-125, 53
-1024 No. 54-74430, No. 54-12
4726@, No. 55-22766, U.S. Patent No. 3,6
No. 42,482, No. 3,488.706, No. 3
, No. 557,066, No. 3,271,147, No. 3,271,147, No. 3,271,147, No.
No. 3,271.148, Special Publication No. 55-29418@,
Same No. 56-36414, Same No. 57-12139
, RD 12045 (1974).
Each II mordant can be mentioned. Particularly useful mordants are polymers containing ammonium salts,
Quaternary amino group described in U.S. Patent No. 3,709,690
Contains polyester. For example, polyamides containing ammonium salts
As a polymer, polystyrene-N, N, N-tree
〇-Hexyl-N-vinylbenzylammonium chlora
id, styrene and vinylbenzylammonium chloride
The ratio of id is preferably 4 to 4:1, more preferably
is 1:1. Typical transfer layers for color patch diffusion transfer contain ammonium salts.
The polymer is mixed with gelatin and coated on the support.
It is obtained by As an example of the heat-resistant organic polymer substance, a molecular weight of 200
0 to 85,000 polystyrene, substituent having 4 or less carbon atoms
Polystyrene derivative with polyvinylcyclohexane
, polydivinylbenzene, polyvinylpyrrolidone, poly
Vinyl carbazole, polyallylbenzene, polyvinyl benzene
alcohol, polyvinyl - formal and polyvinyl
Polyacetals such as butyral, polyvinyl chloride,
Chlorinated polyethylene, Poly W! Chlorinated ethylene, poly
Acrylonitrile, boria N, N-dimethyl 7-lylamine
de, p-cyanophenyl group, pentachlorophenyl group,
and 2,4-dichlorophenyl group-containing polyacrylate
, polyacryl chloroacrylate, polymethyl meth
Acrylate, polyethyl methacrylate, polypropyl
methacrylate, polyisopropyl methacrylate, poly
Lysobutyl methacrylate, poly tert-butyl
methacrylate, polycyclohexyl methacrylate,
Polyethylene glyfur dimethacrylate, poly-2-
Cyano-ethyl methacrylate, polyethylene terephtha
Polyesters such as esters, polysulfone, bisphene
Polycarbonates such as Nord A1 polycarbonate,
Polyanhydrides, polyamides and cellulose
Examples include cetates. Also, Polymer Handbook 2nd
ed, (J. Brandrup, E.H., Imaerou
t 1m) John Wiley & 5ons out
Edition, written in 1! If the tail glass transition temperature is 40℃ or higher,
Synthetic polymers are also useful. These polymeric substances can be used alone or in combination.
A combination of the above may be used as a copolymer. Particularly useful polymers include triacetate, diacetate,
Cellulose acetate such as tate, heptamethylene di
Terephthalic acid with amine, fluorene dipropylamine
and adipic acid, hexamethylenediaminediphenic acid,
Combinations such as xamethylene diamine and isophthalic acid
polyamide, ethylene glycol and diphenyl
Carboxylic acid, bis-p-carboxyphenoxybutane and
Polyester made from a combination of polyethylene glycol, etc.
polyethylene terephthalate, polycarbonate,
Examples include vinyl chloride. These polymers are modified
It may be something like that. For example, cyclohexane dimethyl
Tatool, isophthalic acid, methoxypolyethylene glycol
Cole, 1,2-dicarbomethoxy-4-benzenesul
Polyethylene terephthalate using phonic acid as a modifier
Rates are also valid. Among these, particularly preferred are:
From polyvinyl chloride described in Japanese Patent Application No. 58-97907
and the polycarbonate layer described in Japanese Patent Application No. 58-1286004.
A layer consisting of carbonate and a plasticizer can be mentioned. The above polymer is dissolved in a suitable solvent and applied onto the support.
or a film made of the above polymer.
Can a film-like image-receiving layer be laminated to a support?
, or the above polymers without coating on a support.
The image-receiving layer is composed of a member (e.g., film) consisting of
It can also be used as an image-receiving layer and support. Furthermore, as an image-receiving layer, gelatin is placed on the image-receiving layer on the transparent support.
Opacifying layer containing dispersed titanium dioxide (reflective
It can also be configured by providing a layer). This opacifying layer
, by viewing the transferred color image from the transparent support side of the image-receiving layer.
A reflective color image is expected. The internal latent image type silver halide emulsion in the present invention is, for example,
U.S. Patent No. 1,623,499, U.S. Patent No. 2,399.0
No. 83 and No. 3,297,447.
For example, sulfur, selenium, tellurium compounds, gold, white
Chemistry like gold compounds! ! Sensitizers, tin halides, etc.
chemically sensitized by the use of reducing agents or combinations of these
It's okay if it is. Further, the internal latent image type silver halide emulsion in the present invention can be used as an example.
For example, cyanine pigment, merocyanine pigment, composite cyanine color
base, complex merocyanine pigment, holoporacyanine pigment,
styryl dye, hemicyanine dye, oxonol dye,
Optical sensitizing dyes such as hemioxonol dyes alone or in combination
Optically sensitized may be used in combination with more than one species;
Ascorbic L [1 body, azaindene, cadmium salt,
Organic onium salts, organic sulfonic acids, etc., for example, US patents.
No. 2.933,390, No. 2,937,089, etc.
Supercolor sensitization that does not absorb visible light as described in
Additives having effects can also be used in combination. Research Disclosure N for sensitizing dyes
o, 15162 (November 1976).
I can do that. The heat-developable photosensitive material used in the practice of the present invention has no thermal fogging.
Various methods are applied in combination to prevent this. One of the methods is to use benzotriazole and its derivatives.
Conductors, thiouracils, 1-phenyl-5-merca
Mercapto compounds like puttetrazole, azoles
Thioethers or blocked azolethiones
, disulfides such as persulfur W1 salts, e.g. N-halogens.
Nosuccinimide, N-halogenoacetamide, N-ha
Logenooxacillinone, 31-halogenobenzotriazo
N-halo, such as N-halogenobenzimidazole,
Geno compounds can also be used. Further prevents heat build-up
Other methods include lauric acid, myristic acid, etc.
acids, higher fatty acids such as behenic acid, tetrahalogenophthales
Acids or their anhydrides, benzenesulfonic acid and p-toluene
7-aryl sulfonic acids such as sulfonic acid, p-toluene
Aryl sulfinic acids such as sulfinic acids, or salts thereof
lithium laurate, lithium myristate, behe
Salts such as lithium salts of higher fatty acids such as lithium
can be used as a stabilizer. In addition, salicylic acid,
p-human O-oxybenzoic acid, tetrachlorobenzoic acid, p-
U-converted benzoic acid such as acetamidobenzoic acid, phthalic acid,
Isophthalic acid, trimetic acid, biOmetic acid, 5.5-
Acid stabilizers such as monomethylene bissalicylic acid are also effective.
. As a color toning agent that can be used in the heat development go used in the present invention
For example, JP-A-46-4928 and JP-A-46-607.
No. 7, No. 49-5019, No. 49-5020, No. 4
No. 9-91215, No. 49-107727, No. 50-
No. 2524, No. 50-67132, No. 50-6764
No. 1, No. 50-114217, No. 52-33722
No. 52-99813@, No. 53-1020, No. 52-99813@, No. 53-1020, No.
No. 53-55115, No. 53-76020, No. 53-
No. 125014, No. 54-156523, No. 54-1
56524@, No. 54-156525, No. 54-15
No. 6526, No. 55-4060, No. 55-4061
, Publications such as No. 55-32015 and West German Patent No. 2
, No. 140,406, No. 2,147,063@, No. 140,406, No. 2,147,063@, No.
2.220.618, U.S. Pat. No. 3,080,254
No. 3,847.612, No. 3,782,94
No. 1, No. 3,994,732, No. 4,123,2
Described in the specifications of No. 82, No. 4,201,582, etc.
Phthalazinone, phthalimide,
Bilan, Quinazolinone, N-Hydroxynaphthalene
mido, benzoxazine, naphthoxazinedione, 2
．． 3-dihydro a-phthalazinedione, 2,3-dihydro O
-1,3-oxazine-2,4-dione, oxypyridi
Aminolysine, Hydroxyquinoline, Aminoquino
Phosphorus, isocarbostyryl, sulfonamide, 21-1
-1,3-benzothiazine-2,4-(3)1) dione
, benzotriazine, mercaptotriazole, dimel
captotetrazapentalene, phthalic acid, naphthalene,
Taluimin l! etc., and one or more of these and
Mixtures with imidazole compounds also phthalic acid, nuttal
At least one of Mi 1 grade at or acid anhydride and a lid
Mixtures of Radin compounds, and even Phthalazine and Malein
Combination of acid, itaconic acid, quinolinic acid, and gentisin M@
I can give you some advice. Also, the applicant's patent application
No. 58-189628, specification No. 58-1935414
3-amino-5-mercapto-1゜2 described in the prisoner
．． 4-triazoles, 3-acylamino-5-merca
Pto-1,2,4-triazoles are also effective. Internal latent image type photosensitive silver milk not used in the present invention
The agent keeps the surface sensitivity as low as possible and lowers the minimum
concentration, e.g. thiazoli to impart more stable properties.
salts, azaindenes (typically 40% each)
- and droxy-6-methyl-L 3.3a,7-citra
Zaindene and 1-phenyl-5-mercaptotetrazo
Examples include rules. ), urazol, sulfocatecol
, oximes, nitrones, nido-O-indazoles, etc.
It is preferable to add anti-fogging and stabilizing agents. For these, see, for example, U.S. Patent No. 2.728,66
No. 3, No. 2,839,405, No. 2,566.2
No. 63, No. 2,597,915, British Patent M 62
No. 3,448, No. 8 Mei [111]. The internal latent image type silver halide emulsion used in the present invention includes:
For example, wetting agents such as human O-oxyalkanes, e.g.
Acrylate or alkyl methacrylate
Copolymer with methacrylic acid, styrene
Emulsion polymers such as maleic anhydride semi-alkyl ester copolymers
A water-dispersible single-fine particulate polymer obtained by
film property improvers such as saponin, polyethylene glycol, etc.
Coating aids such as coal lauryl ether, other thickeners
, antistatic agent, gelatin plasticizer, surfactant, pH adjustment
agents, antioxidants, ultraviolet absorbers, dyes, brighteners, molders
and, for example, starch, titanium dioxide, zinc oxide,
Silica, alumina, kaolin, clay, polymethyl meth
Matting agents such as polymer beads such as acrylates
It is optional to add various photographic additives such as. Photographic constituent layers of the heat-developable photosensitive material used in the practice of the present invention
can be hardened with various organic or inorganic hardeners. suitable
As hit 11111 agents, for example, chromium salts, zirco
salts, formaldehyde and mucohalogen acids.
aldehyde type, halotriazine type, polyepoxy compound,
Ethyleneimine, vinyl sulfone, isocyanate
hardeners, carbodiimide-based, acryloyl-based hardeners, etc.
It will be done. Components used in the heat-developable photosensitive material used in the present invention
*i fii are selected from a wide range of monthly interest rates.
It is applied to various supports and supports. This support can generally be of any shape.
However, it is flexible in handling as information recording material.
It is preferable to use a film or sheet.
is used. The material for the support is nitric acid
Lulose, cellulose esters (partially aceticated)
Chilled ones are also good. ) polygonyl acetal, poly
Ethylene, polyethylene terephthalate, polycarbonate
- Plastic films or sheets such as
Filters such as wood, glass, glass, metal such as aluminum, etc.
Examples include bars and sheets. Also, baryta paper, resin coat
Textured paper and waterproof paper can also be used. As a super support,
Clay-treated paper such as art paper or coated paper is most suitable.
or paper sized with polysaccharide etc.
. These supports are coated with the various layers mentioned above.
Or, this support itself may contain some of the components.
be able to. Of course, plastic, glass, metal, etc.
If the components are mixed into the support and evaporated, make sure that their properties are sufficiently
Although there are quite a few difficulties involved in making it work, for example,
In the case of paper-based supports, even support (II
Even if certain components are mixed into the material),
Its effect is exactly the same as when it is present in a layer formed by
It shows. Either the components are incorporated into the support, or
Alternatively, the present invention determines whether it is contained or zested during coating on the support.
Conditions such as a diagram of the real hermit and the necessity and advantage of manufacturing
Therefore, both can be easily implemented. The heat-developable photosensitive material used in the practice of the present invention can be obtained by
Various additives are also used to enhance the image 82 degrees.
be able to. For example, U.S. Patent No. 3.667.959
As described in JP-A-59-84236@
, tetrahydrothiophene-1,1-dioxide, 4-
Hydroxybutanone butylactone, methylsulfinyl methane
-C〇-1-SO- such as tan, sulfamide 11
, or compounds with groups such as -502- are effective.
be. The above compounds can be used in a wide range of applications. Useful I! The same is calculated by converting the coating dry film thickness of photosensitive material into mi.
20% heavier than that! The following is preferable, more preferably 0
．． 1 to 15 weight percent. Additionally, as described in U.S. Patent No. 3,708,304,
Also effective are acetates of dust lead, cadmium, and copper, such as
It is. In particular, M salts of amines, gold alI compounds or hydroxyl
Base-releasing compounds that become alkaline when heated, such as compounds
materials, such as NH4Fe (SO4) λ12H20, etc.
There are also water-releasing compounds that decompose and release water when sea urchin is heated.
Effective as a substance that promotes development and dye release reactions.
be. These accelerators can be used in a wide range of applications.
Ru. The useful range is coating and drying of photosensitive materials In! Convert to weight
The total was 50! Im percent or less is preferable, and
preferably from 0.01 weight percent to 40 weight percent.
- cents. In addition, U.S. Patent No. 3,347,675, Japanese Patent Application Publication No. 1983-
Nos. 57231 and 59-168439
Liglycols, ureas, pyridines, amides, sulfur
Honamides, imides, alcohols, oximes, etc.
At which room temperature the odor is solid, but at what processing temperature is used
The non-hydrated material exhibits a mixed melting point together with the components of
A decomposable thermal solvent is preferably used. The photographic layering of the heat-developable photosensitive material used in the present invention is
Prepare various coating solutions and use the dipping method, air knife method, and curtain coating.
Various coating methods such as cloth method or hopper coating method
The photosensitive material is sequentially placed on the support and dried.
Can be created. Further, if necessary, U.S. Patent No. 2.761.791 and
by the method described in British Patent No. 837.095.
It is also possible to apply two or more layers simultaneously. [Specific Effects of the Invention] As explained above, in the present invention, the surface is capped in advance.
It has an internal latent image type silver halide emulsion layer that is not coated.
After imagewise exposure of a silver halide photosensitive material, substantially no water is removed.
Increasing the surface sensitivity of the silver halide without
A new method for forming positive images has been developed.
I was able to provide it. [Specific Examples of the Invention] The present invention will be explained below according to Examples.
The present Mll is not limited to this. Margin Example 1 The conversion type silver chlorobromide emulsion shown below was prepared. Gelatin 80Q and 1M silver nitrate aqueous solution 200nR
Potassium chloride is added to an aqueous solution containing
Adding 2001 fl of a 1.2 molar aqueous solution of Um over 1 minute,
After 1 minute of physical aging, 1 mol of potassium bromide in water was added.
Added 2ootc of liquid and further performed physical aging for 1 minute.
. After washing with water to remove water-soluble halides,
Add 5 g of latin and add water to make a total volume of 400 l;
Ta. A silver chlorobromide emulsion with an average grain size of 0.15 μm was obtained. This emulsion is hereinafter referred to as [EM-1]. Example 2 The conversion type emulsion grains prepared in Example 1 were used as cores.
A core/shell emulsion was prepared as follows. 17 emulsion [EM-1] 1 of 60”CF silver nitrate in 40h
275 molar aqueous solution and 1 molar aqueous potassium bromide solution 27
5 Mixing of vfl and 30d2 of 1M potassium chloride aqueous solution
silver chlorbromide shell by adding the solution simultaneously over 5 minutes.
After precipitation, water-soluble halides are removed by washing with water.
After that, add 20o gelatin and water to make total @60
01:1. Silver chlorobromide core with average particle size of 0.2 μm/
A shell emulsion was obtained. This emulsion will be referred to as [EM-2] below.
call. Similarly, 400 g of core emulsion [EM-1] was heated at 60°C.
3651 (l) of a 2 molar aqueous solution of silver nitrate and 2 molar of potassium bromide
Molar aqueous solution 365i and potassium chloride 0.2 molar aqueous solution 4
By adding 0v (l) of the mixture at the same time in 15 minutes.
After precipitating the silver chlorobromide shell, it is washed with water to dissolve it in water.
After removing the sexual halide, add 45g of gelatin and add water.
In addition, the total amount was set to 11,200Q. A silver chlorobromide core/shell emulsion with an average grain size of 0.25 μm was obtained.
It was done. This emulsion is hereinafter referred to as [EM-3]. Furthermore, in the same manner, 400 g of core emulsion [EM-1] was
A 1 molar aqueous solution of silver nitrate 275- and a 1 molar solution of potassium bromide at
275 mR of potassium iodide aqueous solution and 0.05 molar of potassium iodide aqueous solution
By adding 251 g of the mixture simultaneously over a period of 5 minutes.
After precipitating the silver iodobromide shell, it is washed with water to make it water-soluble.
After removing the halide, add 20o gelatin and add water.
The total amount was 600 (l). A silver iodochlorobromide emulsion with an average grain size of 0.2 μm was obtained. This emulsion is hereinafter referred to as [EM-41]. Example 3 Using the solution shown below, A silveride core emulsion was prepared. Solution 1-A Ossein gelatin 400% distilled water
400wff1 polyiso
Brobylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol solution 301 KB
r 201N H
NO376112 Solution 1-1 -8A○3 1200 gO,
IN HN○360d Solution to 175 (hR) with distilled water
1-C ossein gelatin 35 gKBr
810g Borisop
Lopyrene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 35- Distilled water
So 1750. ft to 40℃
JP-A-57-92523, JP-A No. 57-9252
Solution 1-At using the mixer shown in specification No. 4
, :32 by simultaneous mixing method of solution 1-B and solution 1-C
It took an addition time of 30 minutes. The addition rate is shown in Table 1 below.
As shown in Figure 2, the concentration increased in a polygonal manner with increasing addition time. The pAg value of solution 1-A was adjusted to 9.0 with 20% KBr aqueous solution.
controlled. The DAQ value is measured using a metal silver electrode double jump.
Measured using a traction-type saturated AQ/AgC4 reference electrode.
Ta. For addition of solution 1-8, 1-C1 and 20% KBr aqueous solution
A variable flow rate roller tube fixed pump was used. The prepared emulsion is washed with water to remove water-soluble halides.
After that, add gelatin 1309 and add water to make a total of 6
000 (L) Silver bromide core with an average particle size of 0.13 μm
An emulsion was obtained. This emulsion is hereinafter referred to as [EM-5]. Table 1 Example-4 [Solution 1-C] of Example-3 was replaced with [Solution 2-C] below.
2 mol% of
A silver iodobromide core emulsion containing silver iodide was prepared. Solution 2-C Ossein gelatin 35 QK 3
r 810 gK
I 23.4 g poly
Isobrobylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 35112
Average of 175,011 tons of distilled water
A silver iodobromide core emulsion with a grain size of 0.11 μm was obtained. below
This emulsion is called [EM-6]. Example-5 [Solution 1-C] in Example-3 was replaced with the following [Solution 3-C].
4 mol% iodine was added in the same manner as in Example-3 except that
A silver iodobromide core emulsion containing silver oxide was prepared. Solution 3-C Ossein gelatin 35 GK B
r810 g K I
46.9 g Polyisobrobylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 351J2 evaporated
Average grain size of 1750d with distilled water
A silver iodobromide core emulsion with a diameter of 0.10 μm was obtained. The following
The emulsion is called [EM-7]. Example-6 Example-3! bromide with an average particle size of 0.13μm manufactured by GL
50 mg of sodium thiosulfate per mole of silver in silver particles
and 101B of potassium chloroaurate per mole of silver,
By heating at 60℃ for 90 minutes, the chemical is applied to the particle surface.
Sensitized. Add stabilizer and water and total fi 1500g (silver 1
molar content). Silver bromide grains subjected to the above chemical sensitization
The internal latent image type silver bromide core/shell emulsion is
It was created using the solution shown below. Solution 4-A Ossein gelatin 5g distilled water
3300J Boliisobrovy
Polyethylene oxydisuccinate sodium salt 10% ethanol solution 1012
Monia 28% aqueous solution 6012 Vinegar 156
% aqueous solution 5011 above chemical sensitization
Silver bromide emulsion 1500 Q solution 4-4 18A○3 2800 ammo
Nia 28% aqueous solution with 220nR distilled water
Set it to 560-. Solution 4-C Ossein gelatin 5gKBr
210g polyisobro
Birene-polyethylene oxydisuccinic acid ester sodium salt 10% ethanol solution 10-distilled water
So set it to 560112. (In 0'C, JP-A-57-92523, JP-A-57-92523,
Using the mixing agitator shown in the specification of -92524,
Solution 5-8 and 5-C were mixed into solution 5-A by simultaneous mixing method.
It took an addition time of 20 minutes. The addition rate is
As shown in Table 2, the addition of
Changed. During the addition of each solution, the pAg fraction was adjusted to 9 with KBr 20% aqueous solution.
．． 0, and the pH value was controlled to 1.5 with a 128% acid aqueous solution.
I controlled it. The pAQ value was measured in the same manner as Example M-3,
I) H value is glass electrode and double junction type saturated A
g/, l (measured using J reference electrode. Addition of each solution
A roller tube constant pump with variable flow opening was used.
. The prepared emulsion is washed with water to remove water-soluble halides.
After that, add 50g of gelatin, add water and make all ffi.
It was set to 2200p. Silver bromide core with average particle size of 0.18μl
/shell emulsion was obtained. Below, this emulsion [EM-81
It is called. Table 2 Example-7 Silver bromide grains with an average grain size of 0.13μ prepared in Example-3
The particle surface was chemically sensitized in the same manner as in Example-6.
. The chemically sensitized silver bromide particles described above are used as the core, and the internal
A latent image type silver iodobromide core/shell emulsion was prepared using the solution shown below.
It was prepared using [Solution 4-B] in Example-6 was replaced with [Solution 5-B] below.
2 in the shell by the same method as in Example-7 except that
Silver iodobromide core/shell emulsion containing mol% silver iodide
Created. Solution 5-C Ossein gelatin 5gK B
r 2100 or less margin K I
5.5 g Polyisobrobylene-polyethylene oxydisuccinate ester sodium salt 10% ethanol solution 10112 vaporized
Make it 560- with stored water. A silver iodobromide core/shell emulsion with an average grain size of 140.18 μm
Obtained. This emulsion is hereinafter referred to as [EM-9]. Example-8 Silver bromide grains with an average grain size of 0.13 μm prepared in Example-3
The particle surface was sensitized by 1 hour in the same manner as in Example-6.
Ta. The chemically sensitized silver bromide particles described above are used as the core, and the internal
A latent image type silver iodobromide core/shell emulsion was prepared using the solution shown below.
It was created by [Solution 4-B] and [Solution 4-B] of Example-6 are as follows.
Addition for 40 minutes instead of [Solution 6:B] and [Solution 6-B]
Same as Example-7- except that additional vIB was added.
An iodine containing 2 mol% heptad silver in the shell by method
A silver oxide core/shell emulsion was prepared. Solution 6-B A! :lNO3770Q Ammonia 28% aqueous solution 605. MA distillation
15401 with water! Solution 6-
C Ossein gelatin 15 (IIK
Br 580QK I
15.1 g poly
Sobrobylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 25.1 distilled
With water 154017 average particle size
A 0.23 μm silver iodobromide core/shell emulsion was obtained. This emulsion is hereinafter referred to as [EM-10]. Example-9 Silver iodide 2 with an average grain size of 0.11 μm prepared in Example-4
silver iodobromide grains containing mol % of thiobromide per mole of silver.
Sodium sulfate 50no and potassium chloraurate per mole of silver
Add 10 mg of aluminum and heat at 60°C for 80 minutes.
The surface of the particles was chemically sensitized. Add stabilizer and water
The total m was 1500o (containing 1 mole of silver). mentioned above
An internal latent image formed by chemically sensitized silver iodobromide grains as a core.
Type silver iodobromide core/shell emulsion using the solution shown below.
Created. [Solution 4-B] and [Solution 4-C] of Example-6 are as follows.
Addition for 25 minutes instead of [Solution 7-B] and [Solution 7-C]
Same method as Example 6 except that addition time was required.
iodine containing 5T nyl% silver iodide in the shell by
A silver oxide core/shell emulsion was prepared. Solution 7-8 A! I NO3353g Ammonia 728% aqueous solution 277d Distilled water
at 705 v (1 solution 7
-C Ossein gelatin 6.3g) (B
r 260gK 1
17,217 Boliiso
Brobylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol solution 101J2 evaporated
With standing water 705. Di average grain
A silver iodobromide core/shell emulsion with a diameter of 0.16 μm was obtained.
. This emulsion is hereinafter referred to as [EM-11]. Example-10 Silver iodide 2 with an average grain size of 0.11 μm prepared in Example-4
Silver iodobromide grains containing mol% were prepared in the same manner as in Actual Example-9.
The particle surface was chemically sensitized. With the silver iodobromide grains subjected to the above-mentioned ibis sensitization as the core,
The internal latent image type silver iodobromide core/shell emulsion was prepared in the following solution.
Created using. [Solution 4-B] and [Solution 4-C] of Example-6 are as follows.
Instead of [Solution 8-B] and [Solution 8-C], for 50 minutes
Same method as Example-6 except that addition time was required.
iodobromide containing 5 mol% silver iodide in the shell by
A silver core/shell emulsion was prepared. Solution 8-B AQ NOa 1013
g Ammonia 28% aqueous solution 795 v
fl distilled water 202611
Solution 8-C Ossein gelatin 18 g) (3
r 700gK I
49.5 g bolii
Sobrobylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 351g distilled
2026vI2 average grains with water
A silver iodobromide core/shell emulsion with a diameter of 0.21 μm was obtained.
. This emulsion is hereinafter referred to as [EM-12]. Example-11 Silver iodide with an average grain size of 0.10μ prepared in Example-5
Silver iodobromide grains containing 4 mol % were added with 1 mol of silver and a transparent chip.
Sodium osulfate 50ma and potassium chlorauric acid per mole of silver
Add 10 mo of aluminum and heat at 60°C for 70 minutes.
The particle surface was chemically sensitized by Add stabilizer and water
The total Q was 1500o (containing 1 mole of silver). mentioned above
The core is silver iodobromide grains that have been chemically sensitized.
An image-type silver iodobromide core/shell emulsion was prepared using the solution shown below.
Created by [Solution 4-B] and [Solution 4-Cl in Example-6 are as follows.
[Solution 9-B] and [Solution 9-Instead of Cl, addition for 25 minutes
Same method as Example 7 except that addition time was required.
Therefore, silver iodobromide containing 8 mol% silver iodide in the shell
A core/shell emulsion was prepared. Solution 9-B AQN03 403g ammonia
A728% aqueous solution 3171p with distilled water
806. +2 solution 9-C Ossein gelatin 7g) (Br
190gK 1
31.50 polyisobrovy
Ren-polyethyleneoxydisuccinate sodium salt 10% ethanol solution 151g distilled
Average particle size 0 to 806d with water
．． 15 μl of silver iodobromide core/shell emulsion was obtained. Below
This emulsion is called [EM-13]. Example 12 Using the silver chloride emulsion shown below as a core, internal latent image type silver chloride
A core/shell emulsion (average grain size 0.2 μm) was prepared. 80a of gelatin and 200d of 7 mol silver nitrate aqueous solution
vl at a temperature of 40°C in an aqueous solution containing ! II t, long
200t12 of potassium chloride 1.2M aqueous solution for 1 minute
Added with. Then wash with water to remove water-soluble halides.
After that, add 5g of gelatin and add water to make the whole @ 4o
og. Silver chloride core particles with an average particle size of 0.15 μm were obtained. Next, the above-mentioned silver chloride particles were added with sodium thiosulfate per mole of silver.
Added 40 u of lithium and 8 mg of chloroauric acid per 1 mmol of silver.
The particle surface was heated at 55°C for 100 minutes.
chemically sensitized. Add stabilizer and water and make 2soog whole teeth
(containing 1 mole of silver). Salt further chemically sensitized
Add 275 mol of silver nitrate aqueous solution to 500 g of silver oxide emulsion at 40°C.
m1' and potassium chloride 1.1 molar aqueous solution 275112
The silver chloride shell was added simultaneously for 10 minutes.
After precipitation, water-soluble halides are removed by washing with water.
After that, add 20Ω of gelatin and add water to make all the teeth 60Ω.
01:1. Internal latent image type chloride with average particle size of 0.2μm
A silver core/shell emulsion was obtained. This emulsion is described below as [EM
-14]. Example-13 [Solution 1-Cl of Example-3 was changed to the following [Solution 10-Cl]
5 mol% by the same method as in Example-3 except that
A silver chlorobromide core emulsion containing silver chloride was prepared. Solution 10-C Ossein gelatin 35gK B
r 800 tJKC
I 26.3g Boliiso
Propylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 351g distilled
Average grain size (1750mj) with water
A silver chlorobromide core emulsion with a diameter of 0.10 μm was obtained. Next, the above-mentioned silver chlorobromide particles were added with sodium thiosulfate per mole of silver.
110 chloroauric acid per 1 g of thorium 5oII and 1 mole of silver
By adding ll1 and heating at 56°C for 100 minutes.
The particle surface was chemically sensitized. Add stabilizer and water to total f.
i1500g (containing 1 mole of silver). Chemistry mentioned above
Internal latent image type salt with sensitized silver chlorobromide particles as the core
Prepare a silver bromide core/shell emulsion using the solutions shown below.
did. . [Solution 9-Cl in Example-11] [Solution 11-Cl
In the shell by the same method as in Example-3 except that
Silver chlorobromide core/shell milk containing 5 mol% silver chloride in
A drug was created. Solution 11-C Ossein gelatin 1gK B
r 1
90 QKCffi
9. Og polyisobrobylene-polyethylene
Renoxydisuccinate sodium salt 10% ethanol solution 151g distilled
Average grain size to 806 in+ with water
A silver chlorobromide core/shell emulsion with a diameter of 0.15 μm was obtained.
. This emulsion will hereinafter be referred to as fEM-15J. Example-14 4-
(diethylamino)-2-methylphenylsulfamine
Acid soda (1, og/l'), surfactant and hardener
The thickness of the coated silver is M 2.00 /V.
Polyethylene terephtha with 150μm undercoating
It was coated on a support and dried. These samples are imaged through a sensitometric optical wedge.
After image exposure, the sample was placed in a 52 pressure-resistant metal container.
Maintained under reduced pressure of 10-2 Torr for 10 minutes using a vacuum pump.
Then, hydrogen gas or ammonia gas is introduced.
Hydrogen gas at 1 atm, 80℃ for 5 minutes, ammonia gas at 1 atm.
The atmospheric pressure was maintained at 30° C. for 5 minutes. Next, remove each sample from the metal container.
It was taken out and developed at 20° C. for 5 minutes with a developer having the composition shown below. [Developer composition] Metol 2.5Q Ascorbyl
10G potassium bromide
1Q Sodium Metaborate
Add 35g water
1! Then, wash and dry at a constant temperature in the usual way.
Ta. For the positive images obtained for each sample, the maximum density (
Measure the values of [)n+ax) and minimum concentration ([1m1n)]
The results are shown in Table 3. As is clear from the following margin table 3 and the following margin table 3, internal latent image type silver halide emulsion
After imagewise exposure of a silver halide photosensitive material having
A good positive image can be obtained by applying sensitization treatment and developing it.
It can be seen that the following can be obtained. Example-15 4-(
diethylamino)-2-methylphenylsulfamic acid
Soda (1, og/f) and the sulfobenzo shown below
Triazole silver salt emulsion (formed silver salt, coating silver ji 2.0
g/f), a surfactant and a hardener, and coated silver concave 4.
．． 1 on a polyethylene terephthalate support with a thickness of 150 μm so that Og/f.
Cloth, dry. These samples are imaged through a sensitometric optical wedge.
After image exposure, the sample was placed in a pressure-resistant metal container for 5 days.
Images were taken for 10 minutes under a reduced pressure of 10-inch tres using a vacuum pump.
then introduce hydrogen gas or ammonia gas
Hydrogen gas was heated to 1 atm, 80-'C for 5 minutes, and ammonia gas
The temperature was maintained at 1 atm at 3.0°C for 5 minutes. Next, each sample was
Removed from the container and developed in the same manner as in Example-14.
It was fixed, washed with water, and dried. For each sample, the obtained po
Measure the maximum density and minimum density values of the image and record the results.
are shown in Table 4. [Preparation of sulfobenzotriazole silver emulsion] 1 s in water
In a mixed solvent of Ov12 and ethanol 150112
and poly(4-vinylgorolidone) 40a. 30 g of 4-sulfobenzotriazole, 1-lyhydroxide
Add 30 g of 5N silver nitrate aqueous solution into a solution of 6 g of silver nitrate and stir.
Add vt2, adjust the pH to 6-8, add water and reduce the total amount e.
An organic silver salt dispersion liquid was obtained as oo12. Similar results were obtained using Table 4 below.) As is clear from Table 4, internal latent image type silver halide emulsion
After imagewise exposure of a silver halide photosensitive material having
A good positive image can be obtained by applying sensitization treatment and developing it.
It can be seen that the following can be obtained. 4-(diethylamino)-2-methylphenylsulfa
Sodium mate (1.0Q/v) and the dye donor shown below
Substance M-1 (0.8 g/f) and surfactant cloth, dried
Ta. [Preparation of gelatin dispersion of dye-providing substance] Having the following structure
The dye-providing substance M-1 is mixed with 100 ethyl acetate (hereinafter referred to as EA).
) 30 g, tricresyl phosphate (hereinafter referred to as T
Heat 15g of CP (called CP) at about 50°C to dissolve it uniformly.
A solution of This solution was mixed with Alkanol XC (DuPont
7.5% gelatin water containing 5% aqueous solution 30-
Add to the solution 400i12, stir and mix, and then
Disperse with a modinizer for 30 minutes to obtain a dye with a retention of 600Q.
A gelatin dispersion of donor material was obtained. Dye-donor substance M-1 These samples were passed through an optical infrared ray for sensitometry and imaged.
After image exposure, the sample was placed in a 52 pressure-resistant metal container.
Maintained under reduced pressure of 1o-2 Torr for 10 minutes using a vacuum pump.
Then, hydrogen gas or ammonia gas is introduced.
Hydrogen gas at 1 atm, 80℃ for 5 minutes, ammonia gas at 1 atm.
The atmospheric pressure was maintained at 30° C. for 5 minutes. Next, remove each sample from the metal container.
Take it out and process it in the development process shown below to create a dye image.
A sample was obtained. Processing process (30℃) Processing time Color development 3 minutes 30 seconds ~ Washing with water
1 minute oO seconds bleach fixing
1 minute 30 seconds 2nd water wash 1 minute O
The composition of the treatment liquid used in each treatment step is as follows.
It's easy. [Color developer composition 4-Amino-3-methyl-N-(β-methanesulfuramide ethyl)aniline sulfate 5g Sodium sulfite
Thorium (anhydrous) 2a sodium carbonate
(-water salt>159 Potassium bromide 19 Benzyl
Alcohol 10112 Add water
11 (p with potassium hydroxide)
-110.2) [Bleach-fix solution composition] Ethylene cyamine diferric ammonium triacetate dihydrate 60 G ethylene
Diamine Tetra Vinegar In 1 Thiosulfate
Monium (7% aqueous solution) 10011 Ammonium sulfite
(40% aqueous solution) Add 27.5d water
12 (oH710 with potassium carbonate
y41! magenta color positive of each sample obtained
Maximum density (Dmax) and minimum density (Dm
in) was measured. The results are shown in Table 5. Similar results were obtained using Table 5 below for margins) As is clear from Table 5 below for margins, internal latent image type silver halide emulsions
After imagewise exposure of a silver halide photosensitive material having
A good positive image can be obtained by applying sensitization treatment and developing it.
It can be seen that the following can be obtained. Example-17 In Examples 1-2 and 6-13! ! 4-
(diethylamino)-2-methylphenylsulfamine
Acid soda (1.2 g/f), as shown in Example-15
Sulfobenzotriazole silver salt emulsion (organic silver salt, coated silver
1i 2.20 /f) and the dye-donating substance C- shown below.
1 (1,2 (1/l')) and coated on the surfactant and special holiday.
Cloth, dry. [Preparation of gelatin dispersion of cyan dye-providing substance 1 Following structure
20g of TCP and 20g of dye-donor C-1log
and EA40n12 to form a homogeneous solution.
did. This solution was mixed with Flukanol X (50i of 5% aqueous solution)
1,5% aqueous gelatin solution containing 1'
After stirring and mixing, use an ultrasonic homogenizer for 30 minutes.
A cyan dye-donor with a yield of 31 soog was dispersed between
A gelatin dispersion was obtained. Cyan dye donor C-1 These samples were imaged through an optical model for sensitometry.
After image exposure, the sample was placed in a 52 pressure-resistant metal container.
Keep under a reduced pressure of 10-2) by a vacuum pump for 10 minutes.
then introduce hydrogen gas or ammonia gas
Hydrogen gas was heated at 1 atm and 80℃ for 5 minutes, and ammonia gas was heated at 1 atm.
The pressure was maintained at 1 atm at 30° C. for 5 minutes. Next, place each sample in a metal container.
and the same development process as shown in Example-16.
A sample with a dye image was obtained. each obtained
The maximum density (Dm) for the cyan color positive image of the sample
ax) and the minimum concentration ([)min) were measured. The results are shown in Table 6. Similar results were obtained using Table 6) As is clear from Table 6 below, the internal latent image type silver halide emulsion
A silver halide photosensitive material with
A good positive image can be obtained by applying sensitization treatment and developing it.
It can be seen that the following can be obtained. Example 18 Methyl was added to the emulsions prepared in Examples 1 to 2 and 6 to 13.
Hydroquinone (1, Oo/f), 4-carboxymethylene
Ru-4-thiazoline-2-thione (0,061 J/f)
, Sulfobenzotriazole silver shown in Example-15
Salt emulsion (organic silver salt, coated silver amount 2, Og/f), 3-
Methyl-1,3,5-pentanetriol (4.0g/
v'), gelatin (3, OIJ/n'), polyvinyl
Nylpyrrolidone average molecule 130,000 (3,0 IJ
/l'), a surfactant and a hardening agent. These samples are imaged through an optical model for sensitometry.
After image exposure, the sample was placed in a pressure-resistant metal container for 5 days.
Maintained for 10 minutes under reduced pressure of 1O-2t-L using a vacuum pump.
then introduce hydrogen gas or ammonia gas
Hydrogen gas was heated at 1 atm and 80℃ for 5 minutes, and ammonia gas was heated at 1 atm.
The pressure was maintained at 1 atm at 30° C. for 5 minutes. Place each of the following samples in a metal container.
Take it out, place it on a heat block, and heat it at 150℃ for 1 minute.
Heat development was performed. About the positive images of each sample obtained
Measure the maximum density (Dmax) and minimum density ([)min)
Established. The results are shown in Table 7. (Similar results were obtained using Table 7 below) As is clear from Table 7 below, internal latent image type silver halide emulsion
After exposure, a silver halide photosensitive material with
A good positive image is obtained by applying sensitization treatment and heat development.
It can be seen that an image can be obtained. Example-19 4-
(diethylamino)-2-methylphenylsulfamine
Acid soda (2.0g/y), shown in actual flow example-15
Sulfobenzotriazole silver salt emulsion (organic silver salt, coating
Silver amount 2. Og/f), dye-donor substance M-2 shown below
(1,5g/f), 3-methyl-1°3°, 5-
Pentanetriol (3,0g/f), and lefty
It was applied onto a support and dried. [Preparation of gelatin dispersion of dye-providing substance] Having the following structure
The dye-providing substance M-2 was mixed with 30 g of 10p ethyl acetate, and
Weigh out 10 grams of licresyl phosphate (TCP) and approx.
Heat this solution at 60°C for 1 minute to make a homogeneous solution.
and 5% Alkanol XC (manufactured by DuPont) as a dispersant.
120 d of 2% gelatin aqueous solution containing 301 g of aqueous solution
After stirring and mixing, use an ultrasonic homogenizer for 10 minutes.
Scattered. Dye-donor substance M-2 JII These samples were passed through an optical model for sensitometry and imaged.
After image exposure, the sample was placed in a 52 pressure-resistant metal container and placed in a vacuum.
A vacuum of 10-2 torr was maintained for 10 minutes with an empty pump.
Then, hydrogen gas or ammonia gas is introduced.
Hydrogen gas at 1 atm, 80℃ for 5 minutes, ammonia gas at 1 atm.
The atmospheric pressure was maintained at 30° C. for 5 minutes. Next, remove each sample from the metal container.
Take it out and place it on a heat block at 150℃ for 1 minute.
Thermal development was performed. Magenta color of each sample obtained
Maximum density (Dmax) and minimum density (Dmax) for positive images
[)min) was measured. The results are shown in Table 8. (Similar results were obtained using the margin table 8 below.) As is clear from the margin table 8 below, the internal latent image type halogen improves performance.
It can be seen that a good positive image can be obtained. Example 20 4-(
diethylamino)-2-methylphenylsulfamic acid
Soda (2, Oa/f), shown in Example-15
Sulfobenzotriazole silver salt emulsion (organic silver salt, coated silver
m2. Oa/f), dye-donating substance Y shown below
-1(1,89/l'), 3-methyl-1°3.5
-Pentanetriol (4,0Q/f), gelati
(3, Op/f), polyvinylpyrrolidone, average
Molecule matrix 30,000 (3,00/f) and surfactant
It was coated onto a support and dried. [Preparation of gelatin dispersion of yellow dye-providing substance] Dissolve 5 g of the following dye-providing substance Y-1 in EA15w di.
This solution contains 151 g of alkanol X05% aqueous solution.
Add to 60 ml of 5% gelatin aqueous solution and stir to mix.
After that, disperse with an ultrasonic homogenizer for 10 minutes to collect
100 g of gelatin dispersion of dye-providing substance was obtained.
Ta. These samples are imaged through a sensitometric optical system.
Place the sample into a 51 pressure-resistant metal container on the image-exposed bond.
Maintained under reduced pressure of 1o-2 Torr for 10 minutes using a vacuum pump.
Then, hydrogen gas or ammonia gas is introduced.
Hydrogen gas at 1 atm, 80℃ for 5 minutes, ammonia gas at 1 atm.
The atmospheric pressure was maintained at 30° C. for 5 minutes. Next, remove each sample from a full-bottomed container.
Take out the thermal transfer image receiving material shown below and the color mentioned above.
Layer the photosensitive materials so that the coated surfaces are in contact and heat them using commercially available heat.
Current copy mate (manufactured by Graphic Corporation)
) at 150°C for 1 minute, then
When the image-receiving material is peeled off, a yellow color appears on the image-receiving material.
A positive transfer image was obtained. [Preparation of image-receiving material for thermal transfer] Polyvinyl chloride-containing latex was placed on photographic baryta paper.
Apply NIPOLG-576 (Nippon Ze: ton IH),
Pass through an atmosphere of 150℃ to form a smooth film.
Then, an image-receiving material was prepared. Yellow of each sample obtained
Maximum density (Qmax) and minimum for color positive images
The concentration ([)min) was measured. The results are shown in Table 9.
did. Similar results were obtained using Table 9 below.) As is clear from Table 9 below, internal latent image type silver halide emulsion.
After imagewise exposure of a silver halide photosensitive material having
A good positive image is obtained by applying sensitization treatment and heat development.
It can be seen that an image can be obtained. Example-21 Samples 61 to 70 prepared in Example-20 were subjected to sensitometry.
After image exposure through a Lee optical model, the sample was
Place it in a pressure-resistant metal container and use a vacuum pump to
Store under reduced pressure for 10 minutes, then add hydrogen gas or
Introducing ammonia gas and hydrogen gas at 1 atm, 80℃ for 5 minutes
During this time, the ammonia gas was stored at 1 atm at 30°C for 5 minutes. Next
Each sample was taken out from the metal container and prepared in Example-20.
The image-receiving material for thermal transfer and the above-mentioned color photosensitive material are applied to the coated surface.
Lay them together so that they are in contact with each other, and use the hot crock pot of Example-20.
, after heating at 150℃ for 5 seconds, 5 seconds with a tungsten light source.
00 lux for 10 seconds, then further 1
Heat at 50℃ for 1 minute! I did @. Peel off the image receiving material.
A color positive transfer image of YeO- is obtained on the image-receiving material.
Ta. The maximum for the obtained color positive image of each sample.
Measure the concentration (Dmax) and minimum concentration (()min)
Ta. The results are shown in the M2O table. Similar results were obtained in the treatment shown in Table 10 of the margin below.) As is clear from Table 10 of the margin below, internal latent image type silver halide milk
After image exposure, the silver halide photosensitive material containing the agent is exposed to gas.
After sensitization treatment and full exposure, heat development
It can be seen that a good positive image can be obtained by
. Example 22 4-(
diethylamino)-2-methylphenylsulfamic acid
Soda (2,0 (1/1'), shown in Actual Example-15
Sulfobenzotriazole silver salt emulsion (organic silver salt, coating
Ginzan 2. Og/f), the dye shown in Example-20
Donor substance Y-1 (1, h/n”), 3-methyl-1,
3,5-pentanetriol (4,Oi; 1/v'
), gelatin (3,Og/1'), polyvinyl
Pyrrolidone average molecule ff130,000 (3,0(1
/f) was coated on an interfacial talate support and dried. These samples are imaged through a sensitometric optical wedge.
After image exposure, the sample was placed in a 52 pressure-resistant metal container.
Maintained under reduced pressure of 10-2 Torr for 10 minutes using a vacuum pump.
Then, hydrogen gas or ammonia gas is introduced.
Hydrogen gas at 1 atm, 80℃ for 5 minutes, ammonia gas at 1 atm.
The atmospheric pressure was maintained at 30"C for 5 minutes. Next, each sample was placed in a metal container.
and then add t-butylaminoborane 0.5% solution.
After drying the sample, heat as shown in Example-20
The coated surfaces of the image-receiving material for transfer and the above-mentioned color photosensitive material come into contact with each other.
15 in the heat development apparatus of Example-20.
After heat development at 0℃ for 1 minute, immediately remove the image-receiving material.
When the material is removed, a yellow color positive image appears on the image receiving material.
Obtained. Yellow color positive image of each sample obtained
The maximum concentration ([)max) and the minimum concentration ([)Il
lin) was measured. The results are shown in Table 11. Similar results were obtained in the processing of the margin table 11 below.) As is clear from the margin table 11 below, the internal latent image type silver halide milk
After image exposure, the silver halide photosensitive material containing the agent is exposed to gas.
A good positive result is achieved by sensitization treatment and heat development.
It can be seen that an image is obtained. Example 23 The following was added to the emulsions prepared in Examples 1 to 2 and 6 to 13 above.
Reducing dye-donor substance M-3 (1,5°/f) shown in
As a base agent, 1-phenyl-4-methyl-4-hydroxy
Dimethyl-3-pyrazolidinone <0.2g/f>, t
-limethylolethane (3,0(]/f), guanidi
Trichloroacetic acid (0,6Q/l'), vinyl pyro
Lydone (1.5g/f>, surfactant and hardener added)
Then coated silver ii12. Thickness so that og / l'
on a 150 μm polyethylene terephthalate support.
Apply and dry. [Preparation of gelatin dispersion of magenta reducible dye-donor
] Dioctyl 30g of the following reducing dye-donor substance M-3
Dissolved in phthalate 30Q and EA90nR, alkano
In 200 tR of 10% gelatin aqueous solution containing Hole XC
After stirring and mixing, use an ultrasonic homogenizer for 3
Reducing dye donor with a yield of 1500o after dispersing for 0 minutes
A gelatin dispersion was obtained. ;? Original dye donor NM-3 These samples were passed through an optical model for sensitometry and imaged.
After image exposure, the sample was placed in a pressure-resistant metal container.
Maintained under reduced pressure of 10-2 Torr for 10 minutes using a vacuum pump.
Then, hydrogen gas or ammonia gas is introduced.
Hydrogen gas at 1 atm, 80℃ for 5 minutes, ammonia gas at 1 atm.
The atmospheric pressure was maintained at 30°C for 5 minutes. Next, remove each sample from the metal container.
I took it out. Next, a 100μm thick undercoat coated with white pigment.
% styrene and N on polyethylene terephthalate support
-benzyl-N,N-dimethyl-N-(3-maleimide
1=1 copolymer of propyl) ammonium chloride
and a receiving material coated with a receiving layer made of acid-treated gelatin.
After immersing the material in water, the coated surface comes into contact with the photosensitive material described above.
After overlapping for 30 seconds, transfer the image receiving material to the photosensitive material.
When you peel it off, a magenta color positive transfer image appears on the image-receiving material.
Obtained. Magenta color positive image of each sample obtained
maximum concentration ([)max) and minimum concentration (pmin
) was measured. The results are shown in Table 12. Similar results were obtained using Table 12 of the margin below.) As is clear from Table 12 of the margin below, internal latent image type silver halide milk
After image exposure, the silver halide photosensitive material containing the agent is exposed to gas.
A good positive image can be obtained by sensitizing the image and developing it.
It can be seen that an image can be obtained. Example-24 Transparent polyethylene terephthalate support with undercoating
Each layer shown below is placed on the supporting body with a thickness of 150 μm from the support side.
Samples were prepared by sequentially applying the following coatings. (1) Blue-sensitive internal latent image type silver halide emulsion layer Example-1
Internal latent image type halogenation shown in Table 13 prepared in ~13
Emulsion with blue sensitized silver particles (silver coating amount: 3.5 g/f>
, 4-(diethylamino)-2-methylphenylsul
Sodium famate (1,”511/f), Example-15
Sulfobenzotriazole silver salt emulsion shown in (silver coating amount
3. sg/12), yellow shown in Example-20
- Dye-donor Y-1 (2,0111/f'), po
Liethylene glycol molecule M300 (3,0!;l
/f), 3-methyl-1,3,5-ben-thantri
All (i, 5g/1'), gelatin (3,00
/f), polyvinylpyrrolidone average molecular weight 30.0
00 (3,0o/f), surfactant (o, osg
/f) and a hardener (0,15Q/f) (2p
Intermediate layer gelatin (1,00/f), polyvinylpyrrolidone
(1,0 g/v), non-diffusible dye donor as shown below
Layer consisting of substance (0,4o/f) Non-diffusible dye-providing substance (3) Green-sensitive internal latent image type silver halide emulsion layer Example-1
The internal latent image type shown in Table 13 prepared in ~2 and 6~13
Emulsion with green sensitized silver halide grains (silver coating 13.5
0/n”), 4-(diethylamino)-2-methylphene
Nilsulfamate sodium (1,2o/f), sulfobe
Zotriazole silver salt emulsion (coated silver 13.5g/f)
Magenta dye-donor substance M-4 (2,0 o/f
> , polyethylene glycol (3.0g/l')
, 3-methyl-1゜3.5-pentanetriol (1,
5CI/l'), gelatin (3,og/f)
, polyvinylpyrrolidone (3,oQ/f), interface
Activator (0,05o/f) and hardener (0,159/f)
n') [gelatin as a magenta dye-providing substance]
Preparation of dispersion J Dissolve 5 g of the following dye-providing substance M-4 in 151 g of EA.
Then, add 151 g of 5% aqueous alkanol XC solution to this solution.
Add to 5% gelatin aqueous solution 60i12 containing and stir
After mixing, disperse with an ultrasonic homogenizer for 10 minutes.
A gelatin dispersion of a dye-providing substance with a yield of 111 oo was obtained.
. Dye-donor substance M-4 (4) Intermediate layer gelatin (1,0!1/f), polyvinyl pylori
Layer consisting of (1,01)/1”)〈5) Red sensitivity
Internal latent image type silver halide emulsion layer Examples 1 to 2 and 6 to
Internal latent image type silver halide prepared in Table 13 and shown in Table 13
Emulsion with red sensitized grains (silver coating 513.OQ /v'
), 4-(diethylamine)-2-methylphenylene
Rusulfamate sodium (1, OQ /v2), sulfamate
Hobenzotriazole silver salt emulsion (silver coating 1i 3.0
o/f), cyan dye-donor substance C-2 shown below (
1,5o/f), polyethylene glycol (2,5o/f), polyethylene glycol (2,5o/f)
f), 3-methyl-1,3,5-pentanetriol (
1,0p/v”), gelatin (2,5o/f), po
Rivinylpyrrolidone<2.5o/f), surfactant
(0,05Q/f) and hardener (0,13/f)
[Made by II of gelatin dispersion of cyan dye-providing substance] The following layer
Dissolve 2.5 g of dye donor C-in EA15- and add
5% gelatin containing Kanol XC 5% aqueous solution 1512
Add to 60 tf of aqueous solution and stir and mix.
Disperse for 10 minutes with a modifier to collect 100g of
A gelatin dispersion of a dye-providing substance was obtained. Dye-donor substance C-2 (6) Protective layer gelatin (1, Oj/v'), polyvinylpyro
Ridone (1, OQ /x'), matting agent (oJg
/v'), surfactant (0.1 g/l') and V
These samples were passed through an optical wedge for centretometry and imaged.
After image exposure, the sample was placed in a 52 pressure-resistant metal container.
Maintained for 10 minutes under reduced pressure of 10-2 Torr using a vacuum pump.
then introduce hydrogen gas or ammonia gas
Hydrogen gas was heated at 1 atm and 80℃ for 5 minutes, and ammonia gas was heated at 1 atm.
The pressure was maintained at 1 atm at 30° C. for 5 minutes. Next, place each sample in a metal container.
Image-receiving material for thermal transfer prepared in actual flow example-20
and the above-mentioned color photosensitive material are overlapped so that the coated surfaces are in contact with each other.
At the same time, after performing heat development at 150℃ for 1 minute, Sumya
Crab receiver @ When the material is peeled off, a multicolor positive is placed on the image receiving material.
A transferred image was obtained. Color positive image of the sample obtained
maximum density ([)max) and minimum density (Dmin)
was measured. The results are shown in Table 13. As is clear from Table 13 in the margin below, internal latent image type silver halide
Even silver halide photosensitive materials with a multilayer structure have good performance.
It can be seen that a good color positive image can be obtained. Example 25 The emulsions prepared in Examples 1 to 2 and 6 to 13 were
The sulfobenzotriazole silver salt emulsion shown in Example-15
Organic silver salt, coated silver! 12.0g/f) and surfactant and
Add hardener and coated silver amount 4. The thickness is Og/f.
On a 150μm polyethylene terephthalate support
Apply and dry. These samples were imaged through the sensitometry moonlight school.
After image exposure, the sample was placed in a 512 pressure-resistant metal container.
Hold under reduced pressure of 10-” Torr for 10 minutes using a vacuum pump.
Then, hydrogen gas or ammonia gas is introduced.
Hydrogen gas at 1 atm, 80℃ for 5 minutes, ammonia gas at 1 atm.
The atmospheric pressure was maintained at 30"C for 5 minutes. Next, each sample was placed in a metal container.
of the extraction (Dmax) and the minimum concentration ([)min)
The values were measured and the results are shown in Table 14. Table 14 in the margin below (in addition, other gases such as sulfur dioxide gas and hydrogen sulfide gas
(Similar results were obtained in the processing using
Halogenated with agent! I! After exposing the photosensitive material to an image,
By applying sensitization treatment and developing, a good point is obtained.
It can be seen that a similar image can be obtained.

Claims (3)

[Claims] (1) After the process of imagewise exposing a silver halide photosensitive material having a silver halide emulsion layer containing internal latent image type silver halide that has not been coupled in advance, the halogenation process is performed without substantially involving water. A method for forming a positive image, comprising the steps of increasing the surface sensitivity of silver, and then developing. (2) Positive image formation according to claim (1), wherein the step of increasing the surface sensitivity of the silver halide without substantially involving water is a hydrogen sensitization step. Method. (3) The step of increasing the surface sensitivity of the silver halide without substantially involving water is a step of sensitizing with ammonia gas. Positive image forming method.