JPS61235831A - High temperature developable photosensitive material - Google Patents

Abstract

PURPOSE:To enhance development speed and sensitivity, and to obtain sufficiently high image density by incorporating a specified photosensitive silver halide emulsion in a photosensitive material. CONSTITUTION:The photosensitive material contains the photosensitive silver halide emulsion represented by the formula shown on the right in which x, y, and z are each a halogen compsn., and x+y+z=100mol%, x is 0-70mol%, y is 30-100mol%, and z is 0-6mol%. As a result, the obtained high-temp. developable photosensitive material can be enhanced in both of development speed and sensitivity and have sufficient high image density and yet be lowered in deterioration of sensitivity during storage.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to high temperature development photosensitive materials. More specifically, the present invention relates to a high-temperature development photosensitive material using silver halide.

Prior art and its problems Photographic methods using silver halide have been traditionally used because they have superior photographic properties such as sensitivity and gradation control compared to other photographic methods, such as electrophotography and diazo photography. It has been most widely used since then.

In recent years, a technology has been developed that allows images to be formed easily and quickly by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. It's here.

Heat-developable photosensitive materials or high-temperature developable photosensitive materials are well known in this technical field, and for information on heat-developable photosensitive materials or high-temperature developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering J (published by Corona Publishing, 1979). 553 pages ~ 5
Page 55, “Video Information J (published in April 1978) 4
Page 0, “Neblett’s Handbook of Photography and Reprography (Neblett+H
andbook of Photography an
Van Nostrand Reinhold Company (Van N
o5trand Reinhold Compant)
In addition to those described on pages 32 to 33 of , U.S. Pat.
No. 152,904, No. 3.301,678, No. 3
, 392,020, British Patent No. 3,457,075, British Patent No. 1.131,108, British Patent No. 1,167.777
No., and Research Disclosure, June 1978, pages 9-15 (HD-17029).

Many methods have already been proposed for obtaining color images. For a method of forming a color image by the combination of an oxidized developer and a coupler, U.S. Pat. No. 3,761,270, a p-7 minofenol-based reducing agent was disclosed in Belgian patent no. 802,519.
No. and Research Disclosure, September 1975, pp. 31-32, sulfonamide phenolic reducing agents are used, and in U.S. Pat. Proposed.

Further, regarding the method of forming a positive color image by the photosensitive silver dye bleaching method, for example, Research Disk Jar 19th April 6th issue, pages 30 to 32 (RD-14433)
, December 1976 issue, pages 14-15 (RD-152
27) and U.S. Pat. No. 4,235,957, useful dyes and bleaching methods are described.

Furthermore, an image forming method based on thermal development using a compound that has a dye moiety in advance and can release a mobile dye in response to or inversely to the reduction reaction of silver halide to silver at high temperatures has been developed in Europe. Patent publication number 76.492, same number 79.05
No. 6, JP-A-58-28928, JP-A No. 58-2600
It is disclosed in No. 8.

These image forming methods have the advantage that images can be obtained easily and quickly compared to conventional wet processing methods. However, in order to obtain clearer images more quickly, it is necessary to develop at a high temperature or accelerate the thermal development process and improve the maximum density.

In addition, various types of silver halide emulsions are known for use in high-temperature development or thermal development, but the high-temperature development or thermal development process is not well understood, and the design direction of silver halide emulsions is not clear. The current situation is that this is not the case.

(2) Purpose of the Invention The purpose of the present invention is to provide a high-temperature development photosensitive material which progresses rapidly in development, has high sensitivity, provides sufficiently high image density, and exhibits little decrease in sensitivity due to storage.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, the present invention uses AgBrCyI2! as a silver halide. (Here, x, y and 2 indicate the halogen composition, x+
y+z=100%, X is from O to less than 70 mol%, y is from 30 mol% to 100 mol%, and 2 is from 0 to 6 mol%) This is a high temperature development photosensitive material characterized by having a silver emulsion.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The high temperature development photosensitive material of the present invention has a photosensitive silver halide emulsion represented by the following chemical formula as silver halide.

AgBr CI I x 1 z Here, x, y and 2 represent the halogen composition, x+y
When +z = 100 mol%, X is 0 to 70 mol% (however, 70 mol% is not included), preferably 20 to 60 mol%; y is 30 to 100 mol%, preferably 40 to 80 mol%: 2 is 0 to 6 mol%, preferably 0 to 2 mol%.

The reason why such a halogen composition is used is that when X is 70 mol% or more, the sensitivity of the photosensitive material decreases greatly over time and the development speed is slow.
This is because if the amount exceeds mol %, the sensitivity of the photosensitive material will decrease significantly over time.

That is, one preferred embodiment of the above-mentioned silver halide in the present invention is as follows.

AgBr, C sentence (where X' and y!
! y' indicates the halogen composition, and! When '+y' = 100 mol%, X' is less than 70 mol%, preferably 20 to
60 mol%, y′ ranges from 30 to less than 100 mol%, preferably 40 to 80 mol%), and AgBr #C-I, Nikode x
y z x", y' and 2" indicate the halogen composition, X"+y
If “+2”=100 mol%, x” is less than 70 mol%, preferably 20 to 60 mol%, and y” is 30 to io
.

Range less than mol%, preferably 40-80 mol%, 2#
is 6 mol% or less, preferably 2 mol% or less).

Silver chlorobromide and silver chloroiodobromide used in the present invention as silver halides in photosensitive silver halide emulsions may have a uniform halogen composition within the grains, but the composition may differ between the surface and the interior. It may also have a multiplex structure (Japanese Patent Application Laid-Open No. 57-154).
No. 232, No. 5B-108533, No. 59-4875
No. 5, No. 59-52237, U.S. Patent No. 4,433.
048 and European Patent No. 100,984).

Also, although they are usually hexahedral particles, the thickness of one particle is 0,
54 m or less, a diameter of at least 0.6 yILm, and an average aspect ratio of 5 or more (U.S. Pat. No. 4,414
, 310, OLS No. 4,435.499, OLS No. 3,241,646A, etc.) or monodispersed emulsions with nearly uniform particle size distribution (JP-A-57-1
No. 78235, No. 58-100846, No. 58-14
829, International Publication No. 83102338A1, European Patent No. 64,412A3 and European Patent No. 83,377A1, etc.)
It may be.

Two or more types of silver halides with different crystal habits, halogen compositions, grain sizes, grain size distributions, etc. may be used in combination.Two or more types of monodispersed emulsions with different grain sizes are mixed to create gradations. can also be adjusted.

The grain size of silver halide in the present invention has an average grain size of o
, ooilm to loILm is preferred, and 0.0
011Lm to 5pm is more preferable.

These silver halide emulsions may be prepared by any of the acidic method, neutral method, or ammonia method, and the reaction method of the soluble silver salt and soluble halide salt is the one-sided mixing method,
Either the simultaneous mixing method or a combination of these methods may be used.
back-mixing method in which particles are formed under silver ion excess, or p
The Chondral double jet method, which keeps Ag constant, can also be used. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Application Laid-open Nos. 55-142329, 55-158124, U.S. Patent No. 3, 650, 7
No. 57, etc.).

Epitaxial junction type silver halide grains can also be used (@Kokai No. 56-16124, U.S. Pat. No. 4.094,
No. 684).

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

In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

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

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and therefore the Tardel water washing method or the precipitation method can be applied.

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

The silver halide emulsion used in the present invention may be a surface latent image type where a latent image is mainly formed on the grain surface or an internal latent image type where a latent image is formed inside one grain. Direct inversion emulsions combining emulsions and nucleating agents can also be used. Internal latent image type emulsions suitable for this purpose are disclosed in U.S. Pat. No. 2,592,250, U.S. Pat.
It is described in No. 41 etc. Preferred nucleating agents for combination in the present invention are U.S. Pat. 276.364 and 0L32,635,316, etc.

As a method for forming the silver halide grains used in the present invention, a known single jet method or double jet method can be used. The fist double jet method can also be used. In addition, a combination of these methods may be used.In any of the above-mentioned silver halide emulsion forming methods, either the known single-stage addition method or multi-stage addition method may be used, and the addition rate may be a constant rate. , or a stepwise or continuous rate change (this could be, for example, a soluble silver salt and/or
Alternatively, there is a method of changing the addition flow rate of these solutions while keeping the concentration of the halide constant, or a method of changing the concentration of soluble silver salt and/or halide in the additive solution while keeping the addition flow rate constant. (or a combination thereof). Furthermore, the stirring method of the reaction solution may be any known stirring method. Also, the temperature of the reaction solution during silver halide grain formation, p
H may be set in any way.

The coating amount of the photosensitive silver halide of the present invention is 1 g in terms of silver.
The range is from Log/rrf to Log/rrf.

Gelatin is advantageously used as a protective colloid and as a binder for other hydrophilic colloid layers used in the preparation of the emulsions of the invention, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, white matter such as albumin, casein, etc.; cellulose derivatives such as hydroethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.; sugar derivatives such as sodium alginate, starch derivatives, etc. ; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

In addition to lime-processed gelatin, acid-processed gelatin and Priten Society of the Science Photography of Japan (Bu
ll, Sac, Sci.

Photo, Japan), Number (No.)
Enzyme-treated gelatin as described in 16° Bee (P) 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In the present invention, a substance capable of reducing silver halide is contained in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as dye-donating substances with reducing properties described below. Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include inorganic reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, poran-amine complexes, hydroquinones, and amine phenols. , catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., as well as T.H. Author: The Theory of the Photographic Process
of the photographic process
+s) Reducing agents described in 4th Ed., pages 291-334 can also be used. Also, JP-A-56-13
No. 8,736, No. 57-40.245, U.S. Patent No. 4
．． Reducing agent precursors such as those described in US Pat. No. 330,617 can also be used.

Combinations of various developers can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0.00% per mole of silver.
0.01 to 20 mol, particularly preferably 0.05 to 10 mol.

In the present invention, an organic metal salt that is relatively stable to light can be used together with the photosensitive silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic metal salt need to be in contact with each other or at a close distance. Among these organic metal salts, organic silver salts are
It is particularly preferably used. When an organic metal salt is used in combination in this way, when the high-temperature development photosensitive material is heated to a temperature of 50°C or higher, preferably 60°C or higher, the organic metal oxidant also undergoes redox using the latent image of silver halide as a catalyst. It is thought that they are involved.

For details, please refer to Japanese Patent Application No. 16-253745.
It is listed on page 20.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

For details, please refer to Japanese Patent Application No. 59-253745 20
-Described on page 24.

In the present invention, silver may be used as an image-forming substance, and various image-forming substances can be used in various ways, and it is particularly preferable to use a dye-providing substance.

The dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. This method using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. The developer and the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. This method using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. Specific examples of developers and couplers can be found, for example, in The Theory of the Photographic Process, by T.H.
photographyCprocess) 4th edition (
4th Ed, ), pages 291 to 334, and pages 354 to 361, and Makoto Kikuchi, "Photo Chemistry," 4th edition (Kyoritsu Shuppan), pages 284 to 295.

Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds can be found in Research Disclosure Magazine, 1978, 5.
Monthly issue, pages 54-58, (RD-16966), etc.

Furthermore, azo dyes used in high-temperature development or heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances.

Specific examples of azo dyes and bleaching methods are described in U.S. Patent No. 4.
No. 235,957, Research Disclosure Magazine, 1
April 976 issue, pages 30-32 (RD-14433
) etc.

Also, U.S. Patent No. 3,985,565, 4. O'2
Leuco dyes described in No. 2,617 and the like can also be cited as examples of dye-donating substances.

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

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

(Dye-X)n-Y (LI) Dye represents a dye group or a dye precursor group; Correspondingly (Dye-X)n
-Creating a difference in the diffusivity of the compound represented by Y,
Alternatively, Dye is released and the released Dye and (Dye
-X) represents a group that has the property of causing a difference in diffusivity between n and Y, n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different. It's okay.

As a specific example of the dye-donating substance represented by the general formula (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.
No. 3,362,819, No. 3,597,200, No. 3.544.545, No. 3.482.972, etc. In addition, a substance that releases a diffusible dye by an intramolecular nucleophilic substitution reaction was disclosed in Japanese Patent Application Laid-Open No. 51-63
No. 818, etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxacilone ring is disclosed in JP-A No. 49-1989.
No. 111,628, etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

In addition, in these methods, development and dye release or diffusion occur in parallel, making it very difficult to obtain images with a high S/N ratio. Therefore, in order to improve this drawback, dye release A method has also been devised in which the compound is made into an oxidized form that does not have the ability to release a dye, is made to coexist with a reducing agent or its precursor, and after development is reduced by the reducing agent that remains unoxidized to release a diffusible dye. Here are some specific examples of dye-donating substances used.

JP-A-53-110,827, Same No. 54-130,927, Same No. 56-164,342, Same 53- No. 35,533 It is described in.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. , No. 330,524, Japanese Patent Publication No. 48-39,165, U.S. Patent No. 3,443,940, etc., and diffusion-resistant by the reaction between a coupler having a diffusion-resistant group as a leaving group and an oxidized form of a developer. Substances that produce sex pigments are described in U.S. Pat. No. 3,227,550 and others.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, we developed a method that does not require a developer.
Dye-releasing compounds that themselves have reducing properties have also been devised.

Typical examples are U.S. Pat. No. 3,928,312, U.S. Pat. No. 4,053,312, U.S. Pat.
No. 59-69839, No. 53-3819, No. 51-
No. 103343, Research Group Disclosure Magazine 17
465, U.S. Patent No. 3,725,062, U.S. Patent No. 3,
No. 728,113, No. 3, 443, 939, and JP-A-58-116537, etc., and the definition in the general formula is also described in the above-mentioned documents.

Any of the various dye-providing substances described above can be used in the present invention, and specific examples of image-forming substances include:
It is described in the patent documents cited above.

In the present invention, the dye-donating substance is U.S. Pat.
They can be introduced into the layers of the photosensitive material by known methods such as the method described in No. 2,027.

Image formation accelerators can be used in the present invention. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes;
It has functions such as promoting the movement of dyes from the light-sensitive material layer to the dye fixing layer, and from a physicochemical function, it has functions such as bases or base precursors, nucleophilic compounds, oils, thermal solvents, surfactants, silver or silver ions. It is classified as a compound that interacts with However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

For details, please refer to Japanese Patent Application No. 59-253745.
- Described on page 55.

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

For details, please refer to Japanese Patent Application No. 59-253745.
It is listed on page 57.

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

Regarding this, Japanese Patent Application No. 59-253745 57-58
There is a description on the page.

In the present invention, an image toning agent may be contained if necessary. Regarding this specific example, please refer to the patent application No. 59-2.
No. 53745, pages 58-59.

The binders used in the present invention can be contained alone or in combination.

A hydrophilic binder can be used for this binder. A specific example of this is described in Japanese Patent Application No. 59-253745, pages 59-60.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other binder layer.
No. 53745, pages 60-61.

The support used in the light-sensitive material and dye-fixing material used in some cases in the present invention is one that can withstand processing temperatures. Details of this are described in Japanese Patent Application No. 59-253745, pages 61-62. ing.

When using a dye-donating substance that releases an image-wise mobile dye in the present invention, a dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer.

For details, please refer to Japanese Patent Application No. 59-253745 62~
It is described on page 63.

Among the photosensitive materials used in the present invention, in particular, the general formula (L
When containing a dye-donating substance represented by l), since the dye-donating substance is colored, an anti-irradiation or anti-halation substance, or various dyes are further included in the light-sensitive material. Although not necessary, filter dyes, absorbent substances, etc. can be included to improve image sharpness.

Regarding this document, please refer to Japanese Patent Application No. 59-253745 6
You can refer to page 4.

The photosensitive material used in the present invention may optionally contain various additives known as high-temperature development or heat-developable photosensitive materials, and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, and an intermediate layer. layer, AH layer, release layer, etc. For various additives, see Research Disclosure Magazine Vol. 1.170. June 1978 No. 1702.
Additives 1 described in No. 9 include additives such as plasticizers, sharpness-improving dyes, AH dyes, sensitizing dyes, matting agents, surfactants, optical brighteners, and anti-fading agents.

The photographic elements of this invention optionally are photosensitive elements that form or release dyes upon thermal development.

It consists of a dye fixing element that fixes the dye.

In particular, in systems that form images by diffusion transfer of dyes, a photosensitive element and a dye fixing element are essential, and in a typical form, the photosensitive element and dye fixing element are separately coated on two supports. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support.

There are two types of forms in which the photosensitive element and the dye-fixing element are formed on separate supports: one is a peelable type and the other is a peelable type. In the case of the former peel-off type, after image exposure or heat development, the coated surface of the photosensitive element and the coated surface of the dye-fixing element are overlapped, and the photosensitive element is immediately peeled off from the dye-fixing element after the transfer image is formed. Depending on whether the final image is of a reflective or transmissive type, the support for the dye-fixing element can be selected to be an opaque support or a transparent support.

In addition, a white reflective layer may be coated if necessary. In the latter type, which does not require peeling, a white reflective layer is interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. This white reflective layer may be coated on any of the dye fixing elements of the photosensitive element 1. The support of the dye fixing element needs to be a transparent support.

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

Another typical form in which a photosensitive element and a dye fixing element are coated on the same support is disclosed in JP-A-56-67840, for example.
Canadian Patent No. 674°082, U.S. Patent No. 3,7
30,718, in which part or all of the photosensitive element is stripped from the 0 dye fixing element.

Examples include those having a release layer coated at an appropriate position.

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

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

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. A combination of a sensitive emulsion layer and an infrared sensitive emulsion layer, a combination of a blue sensitive emulsion layer, a green sensitive emulsion layer and an infrared sensitive emulsion layer, a blue sensitive emulsion layer, a red sensitive emulsion layer and an infrared sensitive emulsion. There are many combinations of layers.

Note that the infrared light-sensitive emulsion layer refers to an emulsion layer that is sensitive to light of 700 nm or more, particularly 740 am or more.

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

Each of the above emulsion layers and/or the non-photosensitive woody colloid layer adjacent to each emulsion layer has a dye-donating substance that releases or forms a yellow woody dye and a magenta woody dye. Alternatively, it is necessary to contain at least one of a dye-providing substance that forms a cyan hydrophilic dye and a dye-donating substance that releases or forms a cyan hydrophilic dye. In other words, each emulsion layer and/or the non-photosensitive woody colloid layer adjacent to each emulsion layer must each contain a dye-donating substance that releases or forms a hydrophilic dye of a different hue. . If desired, two or more dye-providing substances of the same hue may be mixed and used. In particular, if the dye-providing substance is colored from the beginning, the dye-providing substance may be used separately from this emulsion layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention may optionally contain a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, a matting agent layer, etc. auxiliary layers may be provided.

Especially, Ho! ! (PC) usually contains an organic or inorganic matting agent to prevent adhesion. In addition, this protective layer may contain a mordant, a UV absorber, etc.
Each of the protective layer and the intermediate layer may be composed of two or more layers.

The intermediate layer may also contain a reducing agent to prevent color mixing, a UV absorber, and a white pigment such as TiO2.The white pigment may be added not only to the intermediate layer but also to the emulsion layer in order to increase the sensitivity by one level. It's okay.

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

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

Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer.

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

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

One or more of the above layers may include a base and/or base precursor to promote dye transfer, a wood-philic thermal solvent, an anti-fade agent to prevent color mixing of the dyes, a UV absorber, a dimensional stabilizer, etc. Dispersed vinyl compound to increase the properties of
A fluorescent whitening agent or the like may be included.

The binder in the above layer is preferably hydrophilic, and transparent or semitransparent woody colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, dextrin, pullulan,
Synthetic polymeric substances such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers, etc. are used. Especially gelatin,
Polyvinyl alcohol is effective.

In addition to the above, the dye fixing element may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc. depending on the purpose.

These layers may be coated not only in the dye-fixing element but also in the photosensitive element.
No. 06, No. 3,362.819, No. 3,382,
821, Canadian Patent No. 3,415,644, Canadian Patent No. 9
28.559 etc.

Furthermore, it is advantageous for the dye fixing element of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or may be included in a separate layer.

In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element.

As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in the former method include silicon carbide, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTC thermistors, tin oxide, and zinc oxide, and transparent or opaque thin films are made using known methods. be able to. In the latter method, conductive particles such as metal particles, carbon black, and graphite are combined with rubber and synthetic polymers.

It can be dispersed in gelatin to create a resistor with desired temperature characteristics. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, or the like.

An example of the positional relationship between the heat generating element and the photosensitive element is shown below.

Heat-generating element/support/photosensitive element support 7 Heat-generating element/photosensitive element support/heat-generating element/intermediate layer/photosensitive element support/photosensitive element/heat-generating element support/photosensitive element/intermediate calendar/heat-generating element Image in the present invention As the image-receiving layer, there is a dye fixing layer used in high-temperature development or heat-developable color light-sensitive materials, and any mordant can be selected from commonly used mordants, but polymer mordants are particularly preferred. The mordant is a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like.

Regarding polymers containing one vinyl monomer unit having a tertiary amine group, Japanese Patent Application No. 58-169012 and Japanese Patent Application No. 1983
Specific examples of polymers containing one vinyl monomer unit having tertiary imidazolium include Japanese Patent Application Nos. 58-226497 and 5B-2.
No. 32071, US Pat. No. 4,282,305, US Pat. No. 4,115,124, and US Pat. No. 3,148.061.

Preferred specific examples of polymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent No. 2,0
No. 56,101, No. 2.093,041, No. 1,
No. 594,961, U.S. Patent No. 4,124,386;
4.115,124, 4,273,853, 4,450,224, JP-A-48-28.22
It is described in No. 5, etc.

Other preferred specific examples of polymers containing one vinyl monomer unit having a quaternary ammonium salt include U.S. Pat. No. 3,709,690, U.S. Pat. No. 58-166135, No. 58-169012, No. 58-232070,
It is described in No. 58-232072 and No. 59-91620.

In the present invention, coating solutions are prepared for each of the protective layer, intermediate layer, undercoat layer, back layer, and other layers as well as the high-temperature development photosensitive layer, and are applied using the dipping method, the air knife method, the curtain coating method, or the U.S. A light-sensitive material can be prepared by sequentially coating onto a support using various coating methods, such as the hopper coating method described in Japanese Patent No. 3,681,294, and drying.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761.791 and British Patent No. 837.095.

As a light source for image exposure for recording an image on a high-temperature development photosensitive material, radiation including visible light can be used. Light source 1 generally used for normal color printing
For example, in addition to tungsten lamps, 710-gen lamps such as mercury lamps and iodine lamps, xenon lamps or laser light sources, CRT light sources, fluorescent tubes, and 1 light-emitting diode (LED).
) can be used.

The heating temperature in the high-temperature development process can be from 80°C to about 250°C in cases where the development and transfer steps are different, but a temperature of about 10°C to about 180°C is particularly useful.

The heating temperature in the transfer process can be in the range from the temperature in the high-temperature development process to room temperature, but it is more preferable to use a temperature that is approximately 10°C lower than the temperature in the high-temperature development process, especially when a dye transfer aid is applied. When the development and transfer steps are carried out at the same time, the temperature is preferably 50°C or higher, preferably 60°C or higher. As a heating means in the development and/or transfer process, a simple hot plate, iron, hot roller, heating element using carbon, titanium white, etc. can be used.

A dye transfer aid (for example, water) is applied between the photosensitive layer of a high-temperature development photosensitive material and the dye fixing layer of a dye fixing material to promote image transfer. Alternatively, a dye transfer aid may be applied to both, and then the two may be superimposed. Examples of methods for applying the dye transfer aid to the photosensitive layer or the dye fixing layer include the roller coating method or wire bar coating method as described in Japanese Patent Application Laid-open No. 58-55907, and the method described in Japanese Patent Application No. 58-55908. A method of applying water to a dye-fixing material using a water-absorbing member as described, and a method of high-temperature development or between a heat-developable light-sensitive material and a dye-fixing material as described in Japanese Patent Application No. 58-55906. As described in Japanese Patent Application No. 58-5591O, a bead is formed between the water-repellent roller and the dye fixing layer to apply the dye transfer aid. How to apply, etc. Dip method.

Various methods can be used, such as an extrusion method, a method of applying by jetting from pores, and a method of applying by crushing a bod.

The dye transfer aid may be measured in advance and given in an amount within the range as described in Japanese Patent Application No. 58-37902, or
The amount can be adjusted and used by applying sufficient amount and then squeezing it out by applying pressure with a roller or the like or drying it by applying heat.

For example, there is a method in which a dye transfer aid is applied to a dye fixing material using the above method, the excess dye transfer aid is squeezed out by passing between pressurized rollers, and then the material is superimposed on a high-temperature development photosensitive material.

The heating means in the transfer process includes heating by passing between hot plates or heating by contacting with the hot plates (for example, Japanese Patent Application Laid-Open No. 50-62635).
No. 1), heating by rotating and contacting a heated drum or heated roller (for example, Japanese Patent Publication No. 43-10791), heating by passing through hot air (for example, Japanese Patent Publication No. 53-3273)
No. 7), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source using a roller, belt, or guide member (for example, Japanese Patent Publication No. 44-2546), etc. can be used. . In addition, graphite, carbon black,
Layers of electrically conductive material, such as metal, may be applied, and electrical current may be passed through the electrically conductive layers to heat them directly.

The heating temperature applied in the transfer step can be transferred in the range from the temperature in the high-temperature development step to room temperature, but is particularly 60 degrees Celsius or higher, and 10 degrees Celsius higher than the temperature in the high-temperature development step.
A lower temperature is preferred.

The pressure when the high-temperature development photosensitive material and the dye-fixing material are superimposed and brought into close contact varies depending on the embodiment and the materials used, but is 0.1 to 100 kg/c layer 2, preferably 1 to 50 kg.
/c Otori 2 is suitable (for example, Japanese Patent Application No. 58-55691
(described in issue).

Various methods can be used to apply pressure to the high-temperature development photosensitive material and the dye-fixing material, such as passing it between a pair of rollers or pressing it using a plate with good smoothness. Further, the roller and plate used to apply pressure can be heated within a temperature range from room temperature to a temperature in a high-temperature development process.

■Specific effects of the invention According to the invention, silver halide is AgBr CI I (where x% y and x!z 2 represent the halogen composition, and x+y+Z=lo.

mol%, X is 0 to less than 70 mol%, y is 30
Since it has a photosensitive silver halide emulsion expressed by mol % or more and 100 mol % or less, where 2 is from O to 6 mol % or less, development proceeds quickly and has high sensitivity. In addition, a high-temperature development photosensitive material can be obtained which provides a sufficiently high image density and exhibits little decrease in sensitivity due to storage.

This small decrease in sensitivity due to storage is thought to be due to the ability to create the (100) plane, which is considered advantageous for dye adsorption, without a special solvent, and the contribution of the Cl-rich halogen composition.

Furthermore, the rapid progress of development is thought to be due to the fact that the emulsion of the present invention, which has a large solubility product, is advantageous in high-temperature development, which is considered to be mainly a physical phenomenon.

① Specific Examples of the Invention One specific example of the present invention will be shown below, and the effects of the present invention will be explained in more detail.

Example 1 How to prepare silver halide emulsions 1 to 6 will be described (Table 1
).

Add potassium bromide and sodium chloride (potassium iodide may be added if necessary) to a well-stirred gelatin aqueous solution (20 g of gelatin and 8 g of sodium chloride dissolved in 10001i of water and kept at 50°C). (also available)
An aqueous solution 600- containing (0.59 mole in total) and an aqueous silver nitrate solution (0.59 mole of silver nitrate dissolved in 600 water) were simultaneously added at equal flow rates over 50 minutes.
After washing with water and desalting, add 40 g of gelatin and 200 d of water to adjust the pH.
and sodium thiosulfate and 4-hydroxy-6-
Optimal chemical sensitization was performed using methyl-1,3,3a and 7-titrazaindene, respectively. The yield of emulsion is 700
It is g.

Next, how to prepare silver halide emulsions 7 to 9 will be described (Table 2).

A well-stirred gelatin aqueous solution (20 g of gelatin in 100011 I of water).

HO((lb) 25(CH2) 25(CH2) 2
Potassium bromide aqueous solution 60011 and silver nitrate aqueous solution (
Water B.

0.59 mol of silver nitrate dissolved in 0.01lI) was used to obtain pAg of 8.0, 8.6.
The temperature was maintained at 9.2 and added.

After washing with water and desalting, add 40g of gelatin and 200d of water and P
H was adjusted and optimal chemical sensitization was performed using sodium thiosulfate. The yield of emulsion is 700 g.

Next, the preparation of emulsion 10-13 will be described (Table 3).
.

To a well-stirred aqueous gelatin solution (20 g of gelatin and 4 g of sodium chloride dissolved in 100011I of water and kept at 65°C), add potassium bromide and sodium chloride (potassium iodide as necessary). 800 d of an aqueous solution (0.59 mol in total) containing
and 600 id of an aqueous solution containing 0.59 mol of silver nitrate were simultaneously added at equal flow rates over 60 minutes.

At that time, at the same time as the formation of silver halide grains started, a solution prepared by dissolving 16 g of Dye D-2 shown below in 400 cc of methanol was added over 40 minutes during grain formation. After washing with water and desalting, add 40 g of gelatin and 200 d of water to adjust the pH.
Sodium thiosulfate and 4-hydroxy-6-methyl-1
Optimal chemical sensitization was performed using 3.3a and 7-chitrazaindene. The yield of emulsion is 700 g.

Next, we will describe how to make a benzotriazole silver emulsion. 28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3000 d of water. Add this solution to 4
The mixture was kept at 0°C and stirred. Add 17g of silver nitrate to this solution and add 1g of water.
A solution dissolved in 001i was added over a period of 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.30, and a yield of 400 g of benzotriazole silver emulsion was obtained.

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

Weighed 5 g of the following magenta dye-donating substance (B), 0.5 g% of sodium succinate-1-ethyl-hexyl ester sulfonate as a surfactant, and 10 g of tri-iso-nonyl phosphate, and added 30 g of ethyl acetate. In addition,
The mixture was heated and dissolved at about 60°C to form a uniform solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was mixed with a homogenizer for 10 minutes. OOOR
Dispersed with PM. This dispersion is called a magenta dye-donating substance dispersion and a dye-donating substance (B).Next, a method for preparing a photosensitive coating will be described.

a) Silver benzotriazole emulsion 10gb) Silver halide emulsion 1 (same preparation method for emulsions 2 to 13) 15gC) 0.2 of sensitizing dye D-2
% methanol solution (not added in case of emulsion 10~13) 1i d) Dispersion of dye-providing substance 25ge) 5% aqueous solution of the following compound 5dlC9Ht900
@2cH20) a Hf) 10% methanol solution of benzenesulfonamide
5dg) 4-Methylsulfonylphenylsulfonylacetate 10% aqueous guanidine solution 15d or more a) to g) were mixed, and a thickener (eg, polystyrene-p-sodium sulfonate) and water were added to make 1 oad. This solution was applied to a wet film thickness of 50 μs onto a 180-thick polyethylene terephthalate film.

Next, the following protective layer coating composition was prepared.

Protective layer h) 1.0% gelatin 400g1)4
-Methylsulfonylphenylsulfonyl guanidine acetate 10% aqueous solution 240dj) 4% aqueous solution of hardener with the following structural formula 50dCH2=CH-3O2CH2C0N
H-(CH2)2-NHCOCH2502CH=CH2 h) to j) were mixed, a thickener and water were added, and the mixture was heated to 1000 I
I changed it to Ii.

This was coated with the above photosensitive coating material and then further coated with a thickness of 30-
It was coated with. The photosensitive coatings are designated Samples A-M depending on the silver halide emulsions 1-13 used, respectively.

These samples A-M were heated at 500 m using a tungsten light bulb.
~500 through a 600n layer pantone filter
Imagewise exposure was performed for 1 second using Lux. After that, it was placed on a heat block heated to 150°C for 20 seconds, 30 seconds, and 40 seconds, respectively.
Uniform heat development was performed for seconds.

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

Dissolve 10 g of poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride: l:l) in 200-g of water, and add 105 lime-treated gelatin. 100g was mixed uniformly. This mixture was uniformly applied to a wet film thickness of 90 mm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample was used as a dye fixing material having a mordant layer.

Next, after supplying 20 liters of water per 1 m2 to the membrane side of the dye fixing material, the heat-treated coated samples A to M were stacked on the fixing material so that their membrane surfaces were in contact with each other.

After heating on a heat block at 80°C for 6 seconds, the dye fixing material was peeled off from the photosensitive material.

A magenta color image was obtained on the fixed material. The density of this was measured using a Macbeth reflection type densitometer (RD 519). Sensitivity was also determined from this.

The results are shown in Table 4.

Table 4 shows that development progresses rapidly in samples using the emulsion of the present invention, and images with high maximum density can be obtained even with high sensitivity and short-time development.

Fog is also at a level with no problem.

Example 2 Sample ANM of Example 1 was heated at 40°C and 70% RH.
It was stored at 0°C in a dry state for 4 days. Thereafter, the same treatment as in Example 1 was carried out, the concentration was measured, and the sensitivity was determined. These values were compared with the sensitivity of the photosensitive material before being stored under the above conditions, and variations in sensitivity were investigated for each.

The results are shown in Table 5.

Table 5 A (present invention) -0,15-0,05B (present invention)
-0,10+0.05C (invention) -0,
20-0,10D (present invention) -0,150 E (comparison) -0,40-0,25F (present invention)
-0,15-0,10G (comparison) -0,
60-0,25H (comparison) -0,70-0,4
0! (Comparison) -0,85-0,45J (present invention) -0,050 K (present invention) O+0.05 L (present invention) -o,os.

M (comparison) -0,20-0,05 Change in low sensitivity = (Sensitivity before storage) - (Sensitivity after storage) From Table 5, it can be seen that there is no change in sensitivity due to storage in samples using the emulsion of the present invention. You can see that it's small.

Example 3 A color photosensitive material N having a multilayer structure as shown in Table 6 was prepared using the photosensitive silver halide emulsion 2 prepared in Example 1 and the benzotriazole silver emulsion.

The yellow dye-donating substance dispersion has magenta dye-donating properties, except for using yellow dye-providing substance (A) (described later) and using 7.5 g of tricresyl phosphate as a high-boiling solvent. Made in the same way as matter.

The dispersion of the magenta dye-providing substance prepared in Example 1 was used.

A dispersion of a cyan dye-providing substance was prepared using a cyan dye-providing substance (C) (described later) in the same manner as the yellow dye dispersion.

A photosensitive material was prepared in the same manner as in photosensitive material #4N except that the emulsions used in the first layer, WS3 layer, and fifth layer were changed as shown in Table 7. I made 0-R.

The emulsion used was prepared in the same manner as in Example 1. However, when Emulsion 12 was used, no sensitizing dye was added.

A tungsten light bulb is used in the multilayered color photosensitive material, and a G, R1 IR three-color separation filter (G is 500' to 600 nm,
R is a 600-700n+s bandpass filter, I
R was constructed using a filter that transmits 700n1 or more)
Exposure was made for 1 second at 500 lux through the lens.

Then, place it on a heat block heated to 140℃ for 20 seconds.
It was heated uniformly for 30 seconds and 40 seconds.

Next, using a dye-fixing material prepared in the same manner as in Example 1, 20 - of water per 1 m2 was supplied to the film side of the dye-fixing material, and then the film surfaces of the heat-treated photosensitive coatings were brought into contact with each other. Superimposed with fixed material as shown. After heating for 6 seconds on a heat block at 80°C, the dye fixing material is peeled off from the photosensitive material, and yellow, magenta, and cyan colors are deposited on the fixing material, corresponding to the three color separation filters of G, R, and IR, respectively. The image was obtained.

Maximum density (Dmax) and minimum density (D m1n) of each color
was measured using a Macbeth reflection densitometer (RD 519) to determine the sensitivity.

The results are shown in Table 7.

Table 7 shows that the light-sensitive materials using the emulsions of the present invention have high sensitivity.

Example 4 The multilayer photosensitive materials N to R prepared in Example 3 were dried at 40°C, 70% RH and 50°C in the same manner as in Example 2.
The sensitivity of the light-sensitive material after being stored for several days was compared with the sensitivity of the light-sensitive material before storage, and variations in each sensitivity were investigated.

The results are shown in Table 8.

From Table 8, it can be seen that the light-sensitive materials using the emulsions of the present invention show little change in tightness due to storage.

From the above, the effects of the present invention are clear.

Claims (1)

[Claims] Silver halide is AgBr_xCl_yI_z (where x, y and z represent the halogen composition, and x+y+z
= 100 mol%, x is 0 to less than 70 mol%,
1. A high-temperature development photosensitive material comprising a photosensitive silver halide emulsion represented by the following formula: y is 30 mol% or more and 100 mol% or less, and z is 0 to 6 mol%.