JPH01252954A - Thermodeveloping color photosensitive material - Google Patents

Abstract

PURPOSE:To make possible to obtain an image which has high sensitivity and high max. density and low min. density in a short time by dividing a color sensitive emulsion layer into two or more layers having different sensitivities, and specifying the amount of silver contd. in an emulsion layer having the max. sensitivity to 0.1-1 times of the amount of silver contd. in the residual emulsion layer having the same sensitivity to that of said emulsion layer. CONSTITUTION:At least one kind of the color sensitive emulsion layers is divided into two or more layers having the different sensitivities, and the amount of the silver contd. in the emulsion layer having the max. sensitivity is 0.1-1 times of the amount of the silver contd. in the residual emulsion layer having the same sensitivity to that of said emulsion layer. The amount of the silver contd. in the emulsion layer having the max. sensitivity among plural divided layers having the different sensitivities is 0.1-1 times, preferably 0.2-0.8 times of the remaining emulsion layer having the same color sensitivity. Thus, the sensitivity of the sensitive material, without bringing about the deterioration of the max. density and the increase of the min. density, is improved.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a heat-developable photosensitive material that forms an image by heating, and is a 9-positive type heat-developable color photosensitive material with particularly high sensitivity and an improved 8/N ratio. Regarding.

(Conventional techniques) Photography using silver halide has traditionally been the most widely used method because it has superior photographic characteristics such as sensitivity and contrast adjustment compared to other photographic methods such as electrophotography and diazo photography. In recent years, it has become possible to easily and quickly obtain images by changing the image-forming processing method for photosensitive materials using silver halide from the conventional wet processing using seedling liquid, etc. to dry processing using heating, etc. technology has been developed.

Heat-processable photosensitive materials are well known in the art, and for more information about heat-processable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (/FDP, published by Corona Publishing, p. 3)%jj! Published page, 7 months, video information Hiro Q Sada, "Nebuletstu,"
Handbook for Photography Professionals”
7th edition (Nebletts, Handbook of
Photograpby and eorogra
phy 7thEd,) Van Nostrand Reinhold Kan/enie (Van No5Lran
d Reinhold Company), pages 3λ-33, U.S. Patent No. 3.7! λ, No. 90, No. J, 301
．． No. 671, No. 3゜32λ, No. 020, No. 3. G17.
θ7! No., British Patent No. I, i3t, ior, No. 1. /
No. 67゜777 and Research Disclosure magazine No. 17, June 2015 issue, page 1 (RD-/702).

Color g1. There are various ways to obtain information such as Research Disclosure magazine L7, 2017 issue! three~! t page (RD-/G live issue), same year 7 month issue 3θ~32 pages (几D-/≠gu issue 33), U.S. Patent No. j, f#!, 4j! issue, Same 1.≠bu3,0
No. 72, 4t, Hiro 7, No. 67, same! ,! 77, Octopus No. 7, Dohiro, 607, Jto No. 44,!
It has been proposed in No. 00.624, p. 00.624, ay3. All of these methods generate or release dyes by heating to form iron-like distributions of dyes, and are characterized by the ability to obtain image-like distributions of dyes in a short period of time.

(Problems to be solved by the present invention) Heat-developable photosensitive materials have superior characteristics such as being faster and easier to process than color photosensitive materials that use conventional wet processing, and are expanding the field of industrial use. In order to achieve this goal, it is hoped that an improved sensory material with even higher sensitivity and 87N will be realized.

However, since heat-developable photosensitive materials use high temperatures during the development process, photosensitive silver halide is extremely prone to fogging, and in the case of uninvented positive-type photothermographic materials, there is a large difference in width and a decrease in maX. However, it was difficult to achieve both high sensitivity and S/N ratio.

Conventionally, it has been known to divide the same color-sensitive emulsion layer into II number of layers with different sensitivities in order to achieve high sensitivity in color photosensitive materials with a multilayer structure, but in the case of positive photothermographic materials, Although high sensitivity can be obtained by simply dividing the layer into a plurality of layers, the maximum density decreases and the minimum density significantly increases.

A method of increasing sensitivity by adding a dye-donating compound to a layer separate from the light-sensitive emulsion is also known.

Depending on the type of dye-providing compound, a significant decrease in minimum density may occur. In other words, by using a combination of a dye-donating compound that releases a dye when reduced, a diffusion-resistant reducing agent, and a diffusive reducing agent, the oxidized product of the diffusible reducing agent that reduces silver halide becomes a diffusion-resistant compound. sexual reducing agent'tkr
In the method of obtaining a positive dye image by reducing the dye-donating compound with a diffusion-resistant reducing agent that survives R, it is necessary to add a diffusible reducing agent to the silver halide emulsion layer. Since there is a limit to the amount of diffusible reducing agent that can be produced, the diffusion-resistant reducing agent cannot be sufficiently deactivated, resulting in a high minimum dye concentration.

The purpose of the present invention is to obtain a thermal mass image with high sensitivity, high maximum density, and low minimum density in a short time! #! Our purpose is to provide photosensitive materials.

(Means for Solving the Problems) An object of the present invention is to provide at least a binder, a photosensitive silver halide, a reducing agent, and an I! cft.

In a positive slightly heat-developable color light-sensitive material having a dye-providing compound that releases a dye in reverse response to the reduction reaction of silver halide to silver, at least seven color-sensitive emulsion layers have λ or more different sensitivities. A thermally developable color which is divided into layers and is characterized in that the silver wave in the emulsion layer having the highest g degree t- among the layers is O2/-/ times the amount of silver in the remaining emulsion layers having the same color sensitivity. Achieved through sensitive materials.

The present invention is suitable for application to a multilayer, multicolor photothermographic material having at least two different spectral sensitivities on a support. Each color-sensitive layer has a combination of at least a binder, a photosensitive silver halide, a reducing agent, and a dye-donating compound that releases a dye in response to the reduction reaction of the photosensitive silver halide to silver. Depending on the situation, an organic metal salt oxidizing agent or the like may be included. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, three types of 3 Jl dye-donating compounds, each with different color sensitivities, are used to release each of these dyes. It is used in combination with a silver halide emulsion. Examples of these three types of color sensitivity include a combination of blue sensitivity, green sensitivity, and red sensitivity, and a combination of green sensitivity, red sensitivity, and infrared sensitivity. Each color-sensitive layer can be arranged in various arrangements known for conventional color light-sensitive materials.

In the present invention, at least one of the above color-sensitive emulsions is divided into a plurality of layers having mutually different sensitivities and provided on a support. It is divided into a sensitive layer and a low-sensitivity layer, such as 3M. It is desirable that emulsion layers having the same color sensitivity but different sensitivities are adjacent to each other, but a non-light sensitive layer may be present between these layers. All may be divided into multiple layers with different sensitivities.

According to the present invention, the silver 1 of the emulsion layer having the highest sensitivity among the layers divided into layers with different sensitivities is preferably 0.1 to 1 times the silver 1 of the remaining emulsion layers having the same color sensitivity. is 0.2~0
．． It is possible to increase the range by eight times, and increase the sensitivity without reducing the maximum density or increasing the minimum density.

For heat-developable photosensitive materials, 11r! i. Various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a backing layer can be provided.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, and may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The particle size may be dispersed or polydispersed, and may be mixed with a monodispersed emulsion and melted.The particle size is 0.1 to
The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, or tabular with a high 7 spectral ratio.

Specifically, U.S. Patent No. 4,500,62 G whistle 50
g, No. 4.628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (197
Any of the halogenated nail emulsifiers described in Patent No. 132-253159 (1999) and Taichiin Sho No. 132-253159 can be used.

Although silver halide emulsions may be used unripe, they are usually chemically sensitized before use. Sensitive methods can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Taihan Sho No. 62-253159).

The coating type of the photosensitive silver halide used in the present invention ranges from 1B to 10g/*' in terms of silver.

The heat-developable photosensitive material of the present invention has a gradation (average γ) of each color of Yea-17 Zenta and Cyan in the range of 1 to 3, particularly 1.3 to 3.
It is desirable that it be in the range of 2.5.

If it falls within this 1flff, the gradation of each color of yellow, magenta, and cyan may be different, and the gradation is '?' in the middle when the characteristic white line is drawn. H! It may be designed to have one portion of tff.

In the present invention, since the emulsion is divided into layers of different sensitivities, the desired PW level can be achieved by appropriately selecting the degree of dispersion of the silver halide emulsion used in each layer. By using a highly monodisperse emulsion in the high-sensitivity layer, 7-7-(If there is a dark area next to the rIJ4 area on the original screen, light will wrap around from the bright area to the dark area and the dark area will be overexposed. Current 3L) can be prevented. It is also preferable to use an emulsion with a high degree of monodispersity in the low-speed layer because it increases the whiteness of the highlighted portion of the positive III image formed and provides a neat bundle.

In the present invention, an organic metal salt can be used together with the photosensitive silver halide as an oxidizing agent.

Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include U.S. Pat. No. 4,500,626;
There are benzotriazole (2), fatty acids and other compounds described in 53111 and the like. Also, JP-A-60-113235
Silver salts of carboxylic acids having a furkynyl group such as 7enylbropiol acid described in No. 61-24904
Acetylene described in No. 4 is also useful. Two or more types of organic silver salts may be used in combination.

More than 8! The silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg to 1 with silver rIA stirring.
0g/■2 is appropriate.

Various anticapri agents or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) pages 24-25, the nitrogen-containing carbones and phosphoric acids described in JP-A-59-168442, or JP-A-59-111636. The mercapto compounds and metal salts thereof, the acetylene compounds described in JP-A No. 62-87957, etc. may be used.

The silver halide used in the present invention may be spectrally sensitized by a tin dye. The dyes used include cyanine dyes, norocyanine dyes, complex cyanine dyes, complex 70 cyanine dyes, holobo 2-cyanine dyes,
Included are hemin-7ine dyes, styryl dyes and hemioxonol dyes.

Specifically, U.S. Pat. No. 4,617,257, $7I
'jf No. 59-180550, No. 60-140335
No., RDI 7029 (1978), pages 12-13.

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

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. .615,641, patent application 1986-22
6294 etc.).

These sensitizing dyes may be added to the emulsion before or after chemical ripening, or as described in U.S. Patent No. 4,183,
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225.666.

Addition 1 is generally on the order of 10@-1 to 10@-2 moles per mole of silver halide.

Hydrophilic binders are preferably used for the constituent layers of photosensitive materials and dye fixing materials. Examples include those described on pages (2G)i to (28) of JP-A-62-253159. Specifically, transparent or translucent hydrophilic binders are preferred, such as proteins such as gelatin, gelatin derivatives, cellulose conductors, starch, polyesters such as dextran, pullulan, etc.
Examples include natural compounds such as IM, and synthetic polymeric compounds such as polyvinyl alcohol, polyvinyl biaridone, acrylamide polymers, and the like. Also, JP-A-62-2
45260 etc., i.e. -
Homopolymers of vinyl monomers having 〇〇M or 13O,M (M is a hydrogen atom or alkali 4), or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium tutaacrylate, Ammonium methacrylate, Sumikagel L- manufactured by Sumitomo Chemical Co., Ltd.
58) is also used. Two or more of these binders may be used in combination.

When employing a system in which heat development is performed by supplying water, the use of the above-mentioned superabsorbent polymer allows rapid absorption of water. In addition, when a super absorbent polymer is used in the dye fixing layer and its maintenance layer,
It is possible to prevent the dye from retransferring from the dye fixing material to the pond after transfer.

In the present invention, the amount of application of banhgu is 2 times per 1 person.
0g or less is preferable, especially 10. Below, it is appropriate to further reduce the amount to 7 g or less.

The constituent layers (including the back layer) of the photosensitive material or dye-fixing material contain one or more additives for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. Polymer latex can be included. Specifically, JP-A-62-245258 and JP-A-62-136
Any of the polymer latexes described in No. 648, No. 62-110066, etc. can be used. Use polymer latex with a low positive transition point (below 40°C) as a medium for ￥t.
When used in 4M, cracking of the mordant layer can be prevented, and lath transition, I:! If a polymer latex with a high hardness is used for the back layer, an anti-curl effect can be obtained.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. It also includes dye-donating compounds with reducing properties, which will be described later (in this case, other reducing agents may also be used), and although they themselves do not have reducing properties, they can be used as nucleophilic reagents during the development process. A reducing agent precursor that exhibits reducing properties by the action of heat can be used.

Examples of reducing agents used in the present invention include U.S. Pat.
．． Columns 49-50 of No. 500,626, fi4,48
3.914 No. 30-311fl, same No. 4゜330.
No. 617, PIS No. 4,590,152, Japanese Patent Application Publication No. 1983
-Pages (17) to (18) of No. 140335, 57-
No. 40245, No. 56-138736, No. 59-17
No. 8458, No. 59-53831, No. 59-1824
No. 49, No. 59-182450, No. 60-11955
No. 5, No. 60-128436 to No. 60-12843
Up to No. 9, No. 60-60-198540, No. 60-1
．． No. 81742, f31-259253, +32
-244044, 62-131253 and 62
-13125 (up to No. 3, European patent 220.7413
There are reducing agents and reducing agent precursors described in pages 78 to 96 of No. A2.

One or a combination of various reducing agents can be used, such as those disclosed in US Pat. No. 3,039,869.

If a diffusion-resistant reducing agent is used, electron transfer M and/or electron A transfer agent precursor can also be used.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer groups are 1-phenyl-3-pyrazolidones or aminophenols.

Used in conjunction with the electron transfer angle. The diffusion-resistant reducing agent (electron donor) may be one among the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material, and preferably hydroquinones, sulfone 7mide 7enol head, Sulfone 7 midna 7 tolls, W Kaimei 53-110
Examples include compounds described as electron donors in No. 827 and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 0.01 to 20 mol, particularly preferably 0.1 to 10 mol.

The dye-providing compound used in the present invention has the following general formula (L
The expression l) is false.

(Dye-Y)n-Z (L I )Dy
e represents a dye group, a temporally shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents a Correspondingly, a difference is created in the diffusivity of the compound represented by (Dye-Y)n-Z, or Dye is released and diffusion occurs between the released Dye and (Dye-Y)n-Z. Represents a group having the property of causing a difference in gender, and n
represents 1 or 2, and when n is 2, two Dye-Y
may be the same and #JylI.

Specific examples of the dye-donating compound represented by the general formula CLI include the following compounds 1 to 2.
．． No. 819, No. 3,597,200, No. 3.54
No. 4,545, No. 3,482,972, etc., a dye developer in which a hydroquinone developer and a dye component are linked, although this dye developer is diffusible in an alkaline environment. When it reacts with silver halide, it becomes non-diffusible.

■As described in U.S. No. 7F No. 4,503,137, non-diffusible compounds that release diffusible dyes in an alkaline environment but lose that ability when they react with silver halide can also be used. . As an example, U.S. VF7FM
3 p 980.479-”l ”9 C a 3 j
t intramolecular nucleophile r! 8 compounds that release diffusible dyes by monoconversion reaction, described in U.S. Patent No. 4,199,354, etc.
Examples include compounds that release a diffusible dye through an intramolecular rewinding reaction of the inoxacilone ring.

■US time, + No. 4,559,290, European Patent No. 22
As described in No. 0.746A2, Technical Report 17-6199, etc., non-diffusible compounds that release diffusible dyes by reacting with the reducing agent remaining unoxidized during development may be used.

As an example, the molecule after being reduced is described and described in U.S. Patent No. 4,139,389, U.S. Pat. A compound that undergoes a nucleophilic substitution reaction within the molecule and releases a diffusible dye, U.S. Pat.
4025 (1984), etc., a compound that releases a diffusible dye by an intramolecular electron transfer reaction after being reduced, West German Patent No. 3,008,588A, JP-A-56
-142530, U.S. Patent No. 4,343,893,
No. 4,619,884, etc., the single bond is cleaved to r11 to release a diffusible dye after reduction, and diffusion after electron acceptance is described in U.S. Patent No. 4,450,223, etc. nitro compounds that release sex pigments,
Examples include compounds that release a diffusible dye after accepting electrons, as described in US Pat. No. 4,609,610 and the like.

Also, more preferably, European Patent No. 220.7
No. 46A2, Public Assistance Bulletin 87-(5199, g Kaimei 62-
34953, G2-34954, etc., a compound having an N-X bond (X represents oxygen, sulfur R, or nitrogen atom) and an electron-withdrawing group in one molecule, '+y* 1986-
A compound having so, -x (x has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 106885, and a compound having po-x in one molecule described in No.
A compound having a bond (X has the same meaning as above) and an electron-withdrawing group;
Examples thereof include compounds having a -x' bond (X' is synonymous with X or represents -S O2,-) and an electron-withdrawing group.

Among these, compounds having an N-X bond and an electron-withdrawing group in the molecule are particularly preferred.
Compounds (1) to (3) described in 0.746A2, (
7) to (10), (12), (13), (15), (2
3)-(26), (31), (32), (35), (3
6), (4o), (41), (44), (53) to (5
9), (64), (70), and compounds (11) to (23) of Kokai Technical Report 87-6199.

Hydrophobic agents such as dye-donating compounds and diffusion-resistant reducing agents can be introduced into the layers of the photosensitive material by known methods such as the method described in US Pat. No. 12,322,027. In this case, Japanese Unexamined Patent Publication No. 5983154, No. 59-1
No. 78451, No. 59-178452, No. 59-17
No. 8453, No. 59-178454, No. 59-178
455, No. 59 1713457, etc., with a boiling point of 50°C to 16°C, as necessary.
It can be used in combination with a low boiling point growth solvent of 0°C.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10. The amount is preferably 5 g or less. In addition, less than ice per 1g of binder, and even 0.5c
c or less, particularly 0.3 CC or less is suitable.

The dispersibility of polymers described in Japanese Patent Publication No. 51-39853 and U.K. Publication No. 51-59943 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the paint in the form of particles in addition to the above-mentioned method.

When dispersing a hydrophobic compound in a hydrophilic colloid, various surfactants can be used.
The surfactants listed on pages (37) to (38) of No.-157636 can be used.

In the present invention, Ii is applied to the photosensitive material simultaneously with the activation of development.
Compounds that stabilize the I image can be used. For specific compounds preferably used, see U.S. Patent No. 4,
No. 500,626, columns 51-52.

In systems that form images by diffusion transfer of dyes, a dye-fixing material is used together with a light-sensitive material. Even if the dye-fixing material is coated separately on a support separate from the light-sensitive material, The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer may be coated on the same support as in U.S. Pat. No. 4,500,626. The relationship described in column 57 of the above issue is also applicable to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include those described in U.S. Pat. The mordant described in JP-A No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing material may be provided with auxiliary layers such as a WIN retaining layer, a release layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer.

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, JP-A-62-253159, pages 25) and 62
-245253, etc.

Furthermore, various silicone oils (
All silicone oils can be used, from trimethylsilicone oil to modified silicone oil in which various organic groups are introduced into trimethylsiloxane. Examples include:
"Modified silicone oil" issued by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils described in technical data P6-18B, especially carboxy-modified silicone (trade name X-22-
3710) etc. are effective.

Also, Japanese Patent Application Laid-Open No. 62-215953, Japanese Patent Application No. 62-236
The silicone oil described in No. 87 is also effective.

Antifading agents may be used in photosensitive materials and dye fixing materials. Examples of antifading agents include antioxidants, ultraviolet absorbing agents, and certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, 7-el/- compounds (eg, hindered 7-2/-ols), hydroquinone derivatives, hindered amine derivatives, and spiroingen compounds. Compounds described in JP-A-61-159644 are also effective.

In the ultraviolet region, benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,35268j, etc.),
Benzo-7/N-based compounds (JP-A No. 46-2784), Sono et al. *Ij! ! No. 54-48535, No. 62-
There are compounds described in No. 136641 and No. 61-88256. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, U.S. Patent No. 4.241.155,
No. 4,245,018 PJ columns 3-36, No. 4, 2
54. ．． No. 195 No. 3-ag, JP-A-62-17474
There are compounds described in Japanese Patent Application No. 61-88256, pages (27) to (29), Japanese Patent Application No. 62-234 i03, Japanese Patent Application No. 62-31096, and Japanese Patent Application No. 62-230596.

Examples of useful anti-fading agents include special rFR@62-215272
No. (125) to (137) pages.

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material externally, such as a photosensitive material.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent brightener may be used in the light-sensitive material or dye-fixing material. In particular, it is preferable to incorporate the fluorescent brightener into the dye-fixing material or to supply it from outside the light-sensitive material. , VeenkaLarauanJijTI+
e Chemistry or 5yntl+e
tic DyesJPtSV Volume 8, JP-A-61-
Examples include compounds described in No. 143752 and the like. More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, biphenyl compounds, and carbostyril compounds.

Optical brighteners can be used in combination with antifade agents.

As a hardening agent for the constituent layers of light-sensitive materials and dye-fixing materials, US Pat.
1 [, JP-A No. 59-11G+355, No. 62-245
Examples include hardeners described in No. 261 and No. 61-18942. More specifically, aldehyde hardeners (formaldehyde, etc.), azirinone hardeners, epoxy hardeners Hinylsulfone A hard 111m (N,N'-ethylene-bis(vinylsulfonyl 7cetamide) ethane, etc.), Examples include tratyol-based hardeners (such as dinotyrol urea) and polymer hardeners (compounds described in JP-A No. 62-234157, etc.)8 Coating aids are used in the constituent layers of photosensitive materials and dye-fixing materials. Various surfactants can be used for purposes such as improving releasability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are given in JP-A-62-173463 and JP-A No. 32-1.
It is described in No. 83457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
Used for the purpose of preventing static electricity and improving peelability! Typical examples of lfi fluoro compounds that may contain a fluoro compound include those described in Japanese Patent Publication No. 57-9053, columns 8 to 17, Japanese Patent Publication No. 61-20944, Japanese Patent Application Publication No. 62-135826, etc. Examples include hydrophobic fluorine compounds such as fluorine-based surfactants, oil-like fluorine-based compounds such as fluorine oil, or solid fluorine compound resins such as tetra7tethylene resin.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described in No. 6 (page 29), benzoguanamine resin beads, polycarbonate) 8! Patent Application No. 110064/1988 for fat beads, AS resin beads, etc.
There is a compound described in No. 110065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an anti-foaming M1 anti-bacterial agent, colloidal silica, etc. Specific examples of these additives are given in JP-A No. 61-1999.
No. 88256, pages (26) to (32).

In the present invention, an image formation accelerator may be used in the light-sensitive material and/or the dye fixing material. The image formation accelerator may be one that promotes the redox reaction between a silver salt oxidizing agent and a reducing agent, or a dye-donating substance. It has functions such as promoting reactions such as production of dyes, decomposition of dyes, and release of diffusible dyes, and promotion of transfer of dyes from the light-sensitive material layer to the dye fixing layer. They are also classified as base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,678.
, No. 739, columns 38-40.

As a base precursor, there are 8! that are decarboxylated by heat!
These include salts of acids and bases, compounds that release amines by intramolecular nucleophilic substitution reactions, Rossen rearrangement, or Beckmann rearrangement. Specific examples include U.S. Pat. No. 4,511,493,
It is described in Japanese Patent Application Laid-Open No. 62-65'038.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, combinations of poorly soluble metal compounds described in European Patent Publication No. 210,660 and compounds capable of complexing reaction with metal ions constituting this ¥# soluble metal compound (referred to as complex-forming compounds), Japanese Patent Publication No. 61-23245
Compounds that generate bases by electrolysis as described in No. 1 can also be used as base precursors. Unfortunately, the former method is effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

The light-sensitive material and/or dye-fixing material of the present invention always has a constant H
Various development stoppers can be used for the purpose of obtaining images.

The development stopper referred to here is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or a compound that interacts with silver salt to stop development after proper development. It is an inhibitory compound.

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For more details, see JP-A No. 62-253159 (31) - (
It is described on page 32).

As supports for the light-sensitive materials and dye-fixing materials of the present invention, those that can withstand processing temperatures are used. Common examples include paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarpinate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, triacetyl cellulose, or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, synthetic resin valves such as polyethylene, etc. Paper mixed with natural bulbs, Yankee paper, baryta paper, coachite vapor (especially cast-coated paper), metals, fabrics, glass, etc. are attracting attention.

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A-62-253159 (29) to (3)
The supports described on page 1) can be used.

The surface of these supports may be coated with hydrophilic binder, alumina sol, semiconductive metal oxide such as tin oxide, carbon black, or other antistatic agent.

Methods for exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or black film using a printer or enlarger, and copying machines. A method in which the original image is scanned and exposed through a slit etc. using an exposure device, etc., a method in which image information is transmitted via an electric signal to a light emitting diode, various lasers, etc. for exposure, and a method in which image information is transmitted to a CRT, liquid crystal display, electroluminescence, etc. There is a method in which the image is output to an m-image display device such as a display or a plasma display, and exposed directly or via an optical system.

As mentioned above, light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., such as U.S. Pat. No. 4,500,6.
The light source described in No. 26, column 56 can be used.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit the nonlinearity of the jump between polarization and electric field that appears when a strong optical electric field such as a laser beam is applied, such as lithium niobate, potassium dihydrogen phosphate (KDP ), lithium iodate, BaB, O, etc., urea derivatives, nitroaniline derivatives, such as 3-methyl-
2F ropyrinone-N-Oquindo derivatives such as 4-nitropyridine-N-oxide (POM), JP-A-61-5
Compounds described in No. 3462 and No. 62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

In addition, the above-mentioned image information can be obtained from image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Japan Television Signal Standard (NTSC), and original images obtained by dividing them into a large number of pixels using a scanner. Image signal, CG, C
i created using a computer represented by AD
il image signal can be used.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
1-145544 can be used. These conductive layers can also be used as antistatic layers! function.

The heating temperature in the heat development process can be developed at about 0°C to about 250°C, but it is particularly useful to use a heating temperature of about 0°C to about 180°C.The diffusion transfer process of the six dyes is carried out at the same time as the heat development. In the latter case, the heating temperature in the transfer step can be 1II21I from the temperature in the heat development step to room temperature. More preferably, the temperature is up to about 10°C lower than the temperature at .

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, JP-A-59-218443, JP-A No. 61-2380
56, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is 5
The temperature is preferably 0°C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye-fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation promoters can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Also surface active M
1. An antifoggant, a poorly soluble metal salt and a complex-forming compound, etc. may be included in the solvent.

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, or both.

The amount used is a small amount, less than the weight of the solvent corresponding to the maximum swollen volume of the entire coating film (or less than 1, which is calculated by subtracting the weight of the entire coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film). good.

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). It is also possible to use the solvent by incorporating it into the photosensitive material, the dye fixing material, or both in advance, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the light-sensitive material or dye fixing material. l! The aqueous thermal solvent may be incorporated into either the photosensitive material or the dye fixing material.
It may be incorporated in both, *The layer in which it is incorporated may also be an emulsion layer,
Although it may be an intermediate layer, a protective layer, or a dye fixing layer, it is preferably built into the dye fixing layer and/or its 1iJI layer.

Examples of hydrophilic heat solvents include ureas, birinones, amides, sulfonamide necks, imides, alnyls, oximes, and other heterocycles.

Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or transfer process include contacting a heated bubble or plate, a hot plate, a hot blemisher, a heat roller, a halogen lamp heater, an infrared lamp heater, a far-infrared lamp heater, etc. or passing through a high-temperature atmosphere.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1983.
The method described in No. 44, page 27 can be applied.

Any of a variety of thermal development apparatuses can be used to process the photographic elements of this invention.
Apparatuses described in Japanese Utility Model No. 59-177547, No. 59-181353, No. 60-18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

(Example) Example/ The method for preparing the emulsion will be described.

Emulsion (I) Well-stirred gelatin water bath solution (gelatin 20f, sodium chloride jt%N in water AOOd).

Contains 0.02tf of N'-dimethylethylenethiourea 7
100ml of a water bath solution containing 100ml of silver nitrate, 100ml of a water bathing solution containing potassium bromide≠tata and sodium chloride were simultaneously added at equal flow rates over a period of 6a minutes. . In addition, the dye bath solution (I) AOCC described below was added for 30 minutes after starting after adding the silver nitrate water bath solution.
3 minutes! It was added over a period of minutes. After washing with water and desalting, add gelatin JOf1 to pH 4.0, pAg 7. fK was adjusted.

This emulsion was mixed with triethylthiourea in jt'(≠−
Optimal chemical sensitization is carried out by adding hydroxy-6-methyl-1,3,3a-7-chitrazaindene. In this way, 600 ft of a monodisperse cubic silver bromide emulsion (1) having an average grain size of 0.60 μm was obtained.

Emulsion (River) In emulsion CI), set the temperature of the gelatin water bath to js”cI
A monodispersed cubic silver chlorobromide emulsion (II) AO0v of Q, 0 μm was obtained in exactly the same manner except that 100CX2 of the dye bath solution (I) was added.

Emulsion (III) Gelatin of, potassium bromide and HO (CH
2) 28(CH2)xOHO,'I? Contains 6taoC
] contains 1ooy1 of silver nitrate! 00td aqueous solution and potassium bromide 70? Add the entire roost water bath solution for 10 minutes at the same time.
did. The amount of solidified potassium water bath solution added was adjusted to maintain pAgitf,/. In addition, after starting the addition of the silver nitrate water bath solution, the dye bath solution (I) 71:) CC is added from ≠Q!
It took me a minute to join. After washing with water and desalting, it was added to gelatin JOf1 and adjusted to pH 6 and /% pAg 1.7. This emulsion was subjected to extreme chemical sensitization using sodium thioate and chloroauric acid in an AO0CVC. A monodisperse cubic silver bromide emulsion (Ill) with rounded corners and an average grain size of 0.11 μm was prepared.

Emulsion (IV) In emulsion (III), reduce the temperature of the gelatin water bath to 0°
A monodisperse silver bromide emulsion (■
)6009 was obtained.

How to make the dye solution (I) (CHHz)4803Na o, orri and dissolved in 100 yd of methanol.

Emulsion (V) Well-stirred gelatin water bath solution (gelatin 20t, sodium chloride jf, N in 100al water.

A water bath of 10081 containing 100f of silver nitrate in N'-dimethylethylenethiourea o, oily kept at 6!0C) and a water bath of 30011 containing 4c2f of potassium bromide and sodium chloride/Ff. The liquid was added at the same time at an equal flow rate over a period of to minutes. One minute after the completion of the addition, the below-mentioned dye solution (1) POCC was added. After washing with water and desalting, add 30t of gelatin and pHA, O%pAg.
Adjusted to 7.7. This emulsion! At j'c, triethylthiourea and monohydroxy-6-methyl/3°3a-7-chitrazaindene were added to carry out optimal chemical sensitization. In this way, a monodisperse cubic silver chlorobromide emulsion (y)xQoy having an average grain size of 0°60 μm was obtained.

Emulsion (■) In emulsion (V), silver nitrate water bath solution and halogen water bath solution t-
A monodisperse cubic silver chlorobromide emulsion (■) Aooy with an average grain size of O, aO μm was obtained in exactly the same manner except that 1 dye solution (■) 130 mm was added over 30 minutes.

Emulsion (■) A monodisperse silver bromide emulsion (■) tooy of 0.55 μm was obtained in exactly the same manner except that the dye fmKcn) was added to emulsion Cm).

Emulsion (■) A monodispersed silver bromide emulsion (■) toot with O2≠Qμ door was obtained in exactly the same manner except that emulsion (IV) was added to the dye bath solution (If)/JOcc1.

<How to make dye bath solution (II)> 0,/! f/ was dissolved in methanol 1001.

Emulsion ([) Well-stirred gelatin water bath solution (gelatin in water r00rd! f% sodium chloride 3?, N.

Contains N'-dimethylethylthiourea o, oirt7
Add the following water bath solution (I) to 0°C (kept warm).

(II) simultaneously started fA210 and each 2≠min%
Added over 16 minutes. 20 minutes after the addition of step (1) is complete, add CP to the water bath solution 3! After 23 minutes, water bath solution (1M) was added over 30 minutes.

After washing with water and desalting, add 30f of gelatin to pH 6.

pAg7. Adjusted to r. This emulsion was mixed with triethylthiourea and hydroxy-6-methyl-/
,! , 3m-7-chitrazaindene was added for optimal chemical sensitization. Cubic silver chlorobromide emulsion with a kernel-like average grain size of 0°6 μm and a slightly wide distribution (coefficient of variation/I%)
DC) Aooy was obtained.

Emulsion (X) In emulsion (D (), the temperature of gelatin water fga '17j
'(Exactly the same except for keeping warm, average size O6≠
A cubic silver chlorobromide emulsion CX) 4009 having a slightly wide distribution (coefficient of variation of 151/A%) in j .mu.m was obtained.

Emulsion CM) Well-stirred gelatin water bath solution (30?1 gelatin, 22 potassium bromide, 28 HO(CH2) in 100 d of water)
CH2)28(CH2)20HO,J? At the same time, add the following water bath solution CI)% (n) to pAgr
, and was added over 30 minutes while maintaining the temperature at 7. followed by l
Add the specified @acid aqueous solution rCC and then add the following aqueous solution (In)
, l/) was added over 20 minutes while simultaneously maintaining pkgl, 7. After washing with water and desalting, add gelatin 3rf p) 14.

λ, pAgr, and IK were adjusted. The emulsion was added to the 5th & 5th acid) IJ cum, chloroauric acid and ≠-
Optimal chemical sensitization was carried out by adding hydroxy 7-6-methyl'+3138 7-chitrazaindene. In this way, the average particle size o, to μ door monodisperse! Figure-shaped silver iodobromide emulsion (M) 600? I got it.

Emulsion [1] In emulsion (XI), the temperature of the gelatin bath solution! t
The average particle size was 0.
Monodisperse of IIIμ! Faceted silver iodobromide emulsion (kari) AOO91
Profit sentence.

A photosensitive material 101 having the structure shown in the following table was prepared.

Water-bathable polymer (1): Sumikaglu L--t (H) (Sumitomo Chemical @iB) Surfactant (1); Aerosol OT (manufactured by American Cyanamid Co., Ltd. 611 [1 agent: /, λ-bis(vinylsulfonyl) Acetamide) Ethane High-boiling point organic sections Nitricyclohexylphosphonate Ultraviolet absorber tll: CH3 Ultraviolet absorber (2); Ultraviolet absorber (3); Sensitizing dye: Yellow Dye-donating substance: Magenta Dye-donating substance; Cyan Dye-donating substance: Photosensitive materials 102 to 10r shown in the table below were prepared by dividing each photosensitive layer into one layer in Photosensitive material 10/VC (the weight unit is V/m2).

Here, for g″yt material ioλ, the amount of silver in the high-sensitivity layer is 1 times the amount of silver in the low-sensitivity layer, and for photosensitive material 10J, the amount of silver is /, 1 times, and photosensitive material 1
01 is about o and or times, and each is a comparative example.

In the photosensitive material io+, the amount of silver in the high-sensitivity layer is 2 times the amount of silver in the low-sensitivity layer.
73 (approximately 0.67 times), the photosensitive material ioz~107 is l/
≠(0,21 times), which is an example of the present invention.

Silicone oil (1) Surfactant (1)” Surfactant (2) ★ C3F17SO2NCH2COOK 3H7 Surfactant (3) US CH3 CH2C00CH2CHC4H9 Surfactant (5) 0 3H7 C3F17S02N-(CH2CH20-3T6CH2
Water-soluble polymer 121* Dextran (molecular weight 70,000) Mordant fi+” High boiling point organic solvent (1) Rice Leofuostaj (Ajinomoto Co., Ltd.) ■Ill) Matting agent (11" Silica matting agent (21 views benzoguanamine resin (average particle size/jμ) Color W of the above multilayer structure & tungsten bulb used as the original material iot, ior, B with continuously changing concentration ,
5ooo through G, R and gray color separation filters
Exposure was made for 1710 seconds at lux.

While feeding this exposed W&light material at a linear speed of 20 mx/sec, i! d/m" of water was supplied using a wire bar, and immediately thereafter, the dye-fixing material was superimposed so that the membrane surface was in contact with -10/.

Using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was rz''c, the film was heated for %-0 seconds.Next, the photosensitive material was peeled off from the dye-fixing material.

Clear images of blue, green, red, and gray were uniformly obtained on the dye-fixing material in response to the B, G, dark, and gray color separation filters.

The results of measuring the maximum density (Dmax) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part are shown in Table 1.

From the above results, it can be seen that the photosensitive material of the present invention has high sensitivity, high maximum density, and low minimum density, and is excellent in 8/N. Furthermore, it was found that the photosensitive material of the present invention has smoother gradation characteristics and is superior to the photosensitive material IO/.

Furthermore, the effects of the present invention were confirmed even when all the photosensitive layers did not have a two-layer structure but two or one of the evening color photosensitive layer, the green original photosensitive layer, and the red photosensitive layer had a multilayer structure.

Furthermore, even when each photosensitive layer is divided into a three-layer structure (a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer) instead of a two-layer structure, the sensitivity of the photosensitive material having the structure of the present invention is the same.

It was confirmed that both 8/N were excellent.

Claims (1)

[Claims] In a positive heat-developable color photosensitive material having on a support at least a binder, a photosensitive silver halide, a reducing agent, and a dye-donating compound that releases a dye in reverse response to the reduction reaction of the photosensitive silver halide to silver. , at least one color-sensitive emulsion layer is divided into two or more layers having different sensitivities, and the silver amount in the emulsion layer having the highest sensitivity among them is the same in the silver amount in the other emulsion layers having the same color sensitivity. 1. A heat-developable color photosensitive material, characterized in that it is 0.1 to 1 times as large.