JPS61294428A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To form an image having high quality by providing at least a photosensitive silver halide emulsion and specific comp. on a base. CONSTITUTION:At least the photosensitive silver halide emulsion and the compd. expressed by the formula (I) are provided on the base. The silver halide emulsion may be used in the un-post-cured state and is normally used after chemical sensitization. A sulfur sensitization method, reduction sensitization method and base metal sensitization method may be used alone or in combination with the emulsion for the ordinary type photosensitive material. The amt. of the photosensitive silver halide to be coated is in a 1mg-10g/m<2> range in terms of silver. The photosensitive silver halide is preferably used in combination with an org. metallic salt relatively stable to light, more particularly an org. silver salt as an oxidizing agent. The development can be thereby stopped during the adequate development without decreasing the image density and the image having the high quality is formed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable light-sensitive material, and particularly to a heat-developable light-sensitive material that exhibits stable photographic properties after development.

Prior art and its problems - Photography using silver halide has been the most popular since it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods, such as electrophotography and diazo photography. It has been widely used. In recent years, a technology has been developed that allows images to be easily and quickly obtained 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 has been.

Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979), pages 553-555, and Image Information, published in April 1978, page 40. , Nebletts Handbook of Photography and Rebrography
PhoLograph and Reprograph
y) 7th edition (7th, Ed,) (Van Nostrand Reinhold Campa = -(Van Nostrand
5trand Re1nhold Company)
), pages 32-33 of U.S. Pat. No. 3,152,904,
No. 3,301,678, No. 3,392.020, No. 3,457,075, British Patent No. 1,131,
No. 108, No. 1,167.777, and Research Disclosure Magazine, June 1978 issue, pages 9-15 (R
D-17029).

Many methods have been proposed for obtaining color images. A method for forming a color image by the combination of an oxidized developer and a coupler is described in U.S. Pat. No. 3,761,270 describes P-aminophenol reducing agents as described in Belgian Patent No. 802.519 and Research Disclosure September 3, 1975.
On page 1.32, a sulfonamidophenolic reducing agent is proposed, and in US Pat. No. 4,021,240, a combination of a sulfonamidophenolic reducing agent and a 4-equivalent coupler is proposed.

Further, regarding the method of forming a positive color image by photosensitive silver dye bleaching method, for example, Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-1443
3), December 1976 issue of the same magazine, pages 14-15 (RD-1
5227) and US Pat. No. 4,235,957, useful dyes and bleaching methods are described.

Furthermore, an image forming method by thermal development using a compound that has a dye moiety in advance and releases a mobile dye in response to or inversely to the reduction reaction of silver halide to silver at high temperatures has been patented in Europe. Publication No. 76.492, Publication No. 79,05
No. 6, JP-A-58-28928, JP-A No. 58-26008
Disclosed in the issue.

In many cases, such heat-developable photosensitive materials are developed by applying heat using a base as a development accelerator. If the temperature is too high, the image quality will deteriorate, and even if the heating pattern is the same, the external temperature, heating temperature,
There are variations in the progress of development due to subtle changes in conditions such as the moisture content of the photosensitive material and the time.

As a means to prevent such variations, the patent application 1983-
The esters described in Nos. 85836 and 59-180915, etc., which react with the base immediately after proper development to reduce the base concentration in the film, are very effective, but the reaction products alcohols and phenols There was a problem that some of them volatilized during heat development and caused contamination of processing equipment.

■ Purpose of the invention The purpose of the present invention is to be able to stop development during proper development without reducing image density, and to form high-quality images without adverse effects such as environmental pollution. The purpose of the present invention is to provide a heat-developable photosensitive material.

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

That is, 11 the present invention is a heat-developable photosensitive material containing at least a photosensitive silver halide emulsion and a compound represented by the following general formula (I) on a support.

General formula (I) R1-0-Ar1 -L-Ar2 -0-R2 (in the above general formula (I), R1 and R2 represent the irises (here, R3 and R4 are each a substituted or unsubstituted alkyl group) , aryl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group or heterocyclic residue).

Arl and Ar2 each represent a substituted or unsubstituted arylene group.

L represents a substituted or unsubstituted divalent linking group or a simple bond. ) ■Specific structure of the invention Below, the specific structure of the present invention will be explained in detail.

The heat-developable photosensitive material of the present invention contains a compound represented by the following general formula (I).

general formula %formula% In the above general formula (I), R1 and R2 are represented.

Here, R3 and R4 each represent a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, or a heterocyclic residue.

The alkyl group of R3 and R4 has 1 to 18 carbon atoms.
A straight chain or branched alkyl group is preferable, specifically a methyl group, ethyl group, n-propyl group, n-butyl group, n-butyl group, etc.
Examples include -hexyl group, n-heptyl group, 2-ethylhexyl group, %n-decyl group, and n-dodecyl group.

Substituents for substituted alkyl groups include halogen atoms, alkoxy, aryloxy groups, cyano groups, alkyl or arylthio groups, substituted or unsubstituted carbamoyl groups, alkyl or arylsulfonyl groups, and disubstituted alkyl or aryl groups. Examples include an amino group, a nitro group, and a substituted or unsubstituted sulfamoyl group.

The cycloalkyl group is preferably a 5- or 6-membered cycloalkyl group having 5 to 10 carbon atoms, and specific examples include a cyclopentyne group and a cyclohexyl group.

Examples of alkenyl groups include vinyl, allyl, crotyl, substituted or unsubstituted styryl, and the like.

Examples of alkynyl groups include propionyl groups, substituted or unsubstituted phenylpropionyl groups, and the like.

Examples of aralkyl groups include benzyl group and β-phenethyl group.

As the aryl group, an aryl group having 6 to 18 carbon atoms is preferable, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, and the like. Substituents for the substituted aryl group include a jδ-substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group,
Disubstituted amino group, acylamino group, sulfonylamino group, cyano group, nitro group, alkyl or arylthio group, alkyl or arylsulfonyl group, oxycarbonal group, carbonyloxy group substituted with halogen atom, alkyl group or aryl group , a hydroxyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, and the like.

The heterocyclic residue is preferably a 5- or 6-membered heterocycle containing oxygen, nitrogen, or sulfur as a heteroatom, examples of which include pyridyl group, furi residue, chenyl group, pyrrole group, indolyl group, etc. can be mentioned. Further, this heterocyclic residue may have a substituent shown as an example of the substituent for the above-mentioned substituted aryl group.

Further, Ar1 and Ar2 each represent a substituted or unsubstituted arylene group.

Preferred examples of these include the same substituted or unsubstituted aryl groups listed above for R3 and R4, but with one hydrogen atom removed.

L represents a substituted or unsubstituted divalent linking group or a simple bond.

Among these, the following two connecting groups or a simple bond are preferable.

-C: lI2-0- ([112) H2-1 to n-0-
-C112-Q-CII2-, -CH2-0
- to H2 (wherein, R5 and R6 each represent a hydrogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, or aryl group, and n represents an integer of 1 to 12). Specific examples of the compound represented by (I) are shown below, but are not limited to -R=-0
Lang Huixian (2) In compound (1) -R=CH3σ) Ihii 1000 Ka (3) In compound (1) -R=-CH2Cff1 compound (4) In compound (1) -R=-Q-cH3 (7) Ihi ability (5) Compound (7) where -R=()C)i (C)i3 )3 in compound (1) (6) Compound (7) where -R=OCH(CH3)2 in compound (1) In compound (1) -R=OCM Compound (8) In compound (1) (9) In compound (1) -R=(>-N 02 compound (lO) In compound (1) -R=-Q -CN compound (11) -R=-0-OCHs compound (12) in compound (1) (13) in compound (1) a=-c>NHCCH3σ) ) In compound (1), -R=OS02 NH2 (D(EzoH) (15) In compound (1), -R=()C-CH3 However, -R=-0, Chin (17) Compound Compound (I8) with -R=-CH3 in (16) Compound (19) with -R=- in compound (16) Compound (20) with -R=- in compound (16) In (16), -R=9 (Ibihisen, but -R=-Q) (22) In compound (21) -R=-CH3 compound (23) In compound (21) -R=-C2H5 Compound (24) in compound (21) -R=-C)CH3 compound (25) in compound (21) -R=()Cffi compound (26) in compound (21) (27) compound (21) In -R=()Noz σ) Ihii 1 Science-(28) In compound (21) -R=OCN(7)(is a rumor (29) In compound (21) -FL=-CC13(7)( Hibari (30) In compound (21) -R=-C7) (tsσ) Ihidai 1 course (31) In compound (21) -R=-C7F15 (7) Ihiiya Gakkebutashi -R=-
0 Compound (33) Compound (32) with -R co() Compound (38) Compound (37) -R=-CH3 Compound (39) Compound (37) -R=-CH20() In compound (37), -R=-CH2CJZ However, -R-CH3 compound (44) In (43), -R=-C7H15 compound (45) In (44), -R = -CIs H31 (53) 5Oz (-(1)OSO2-R) However, -R=-CH3 compound (54) -R=0 in compound (53) (55) -R=- in compound (53) OCH3 (56) -R=-OCR in compound (53) A synthesis example of a compound represented by general formula (I) is shown below.

Δ 1 Δ 4 of 4 di(p-hydroxyphenyl)sulfone 25g (0,
A methylene chloride solution (250 mffi) containing 30 cmB of triethylamine (30 cmB of triethylamine) was cooled to about 10°C and stirred, and p-toluoyl chloride (95%) was added thereto.
1 g (0.21 mol) was added dropwise. During the dropping, white crystals were deposited. After stirring at room temperature for 30 minutes,
250 mft of methanol was added, and the precipitate was collected by filtration and washed with methanol. The crude crystals thus obtained were recrystallized from a mixed solvent of N,N-dimethylformamide (DMF") and ethyl acetate (v/v"l/I) to obtain compound (4).
42.1 g (0.81 mol) were obtained.

Yield: 81% Melting point: 241-242°C Δ 2 8 1 Δ In Synthesis Example 1, the reaction was carried out using benzoyl chloride instead of p-toluoyl chloride, and the same procedure was carried out to obtain 34.1 g of compound (1) ( 0,0695 mol) was obtained.

Yield 70% Melting point 244-245°C Δ 3 Δ 5 -4 In Synthesis Example 1, p-chloride was used instead of toluoyl chloride.
(t-butylbenzoyl) and the same operation was performed thereafter to obtain 41.1 g (0,068 mol) of compound (5).

Yield 68% Melting point 225-226°C Δ 4 Δ 26 2.2-di(p-hydroxyphenyl)propane 23
g (0.1 mol), triethylamine 2811II
About 1 acetonitrile solution (250 mffi) containing L
The mixture was cooled to 0° C. and stirred, and 35 g (0.2 mol) of p-chlorobenzoyl chloride was added dropwise thereto. Crystals precipitated during the dropwise addition.

After stirring for 1 hour at room temperature, methanol 300I
IIIL was added, and the precipitate was collected by filtration and washed with methanol. The crude crystals thus obtained were recrystallized from a mixed solvent of isopropyl alcohol and ethyl acetate (V/V-371),
40.0 g (0,079 mol) of compound (26) was obtained.

Yield: 79% Melting point: 158-160°C The amount of the compound of the present invention to be used varies depending on the compound and the system used, but is generally 50% by weight or less in terms of the weight of the coating film. Preferably, the range is 30% by weight or less. Further, the compounds of the present invention can be used alone or in combination of two or more. Furthermore, it is also possible to use a development stopper or a development stop technique other than the one of the present invention.

The compound of the present invention can be dissolved in a water-soluble organic solvent (for example, methanol, ethanol, acetone, dimethylformamide) or a mixed solution of this organic solvent and water, and then incorporated into the binder.

The compound of the present invention can also be incorporated into a binder in the form of fine particles according to the method described in JP-A-59-174830.

Preferably, the compound of the present invention contains 80% of the added compound by the time of proper development (time just before fog increases).
The following decomposes, preferably 50% or less, more preferably 20% or less.

Various bases or base precursors are used in the present invention.

The base or its precursor can be used in either light-sensitive materials or dye-fixing materials.

It is especially advantageous to use a base precursor when it is included in a light-sensitive material.

The base precursor referred to here is one that releases a basic component upon heating. The basic component released may be an inorganic base or an organic base as described below.

Examples of preferred bases include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary and tertiary phosphates, borates, carbonates, quinolates, metaborates: ammonium hydroxide; Materials: Quaternary alkylammonium hydroxides: Other metal hydroxides, etc. Examples of preferred bases include organic bases such as aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those with a pKa of 8 or more are particularly preferred in the present invention. Useful.

Base precursors include salts of organic acids and bases that decarboxylate and decompose when heated, compounds that decompose through Rossen rearrangement, Beckmann rearrangement, etc. and release amines, and other compounds that cause some kind of reaction when heated and release bases. things are used.

Preferred base precursors include precursors of the aforementioned organic bases.

For example, trichloroacetic acid, propiolic acid, cyanoacetic acid,
Examples include salts with thermally decomposable organic acids such as sulfonylacetic acid and acetoacetic acid, and salts with 2-carboxycarboxamide described in US Pat. No. 4,088.496.

Specific examples of preferred bases are shown below, but the base is not limited to these compounds.

Lithium hydroxide, sodium hydroxide, potassium hydroxide,
Barium hydroxide, sodium carbonate, potassium carbonate, sodium quinolinate, potassium quinolate, dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tribasic potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, Sodium metaborate, potassium metaborate, borax, ammonium hydroxide, tetramethylammonium, tetrabutylammonium, ammonia, M
eNH2 (Me represents CH3. The same applies below), Me2
NH1EtNH2 (Et represents C2H5. The same applies below), Et2 NH2, C4Hg NH2, (C4H9)
-2N Hl(HOC2H4)2 NH1Et2 NC
H2CH20H, H2NC2H4NH2, MeNHC2
H4NHMe, Me2 NC2H4NH2, H2NC3
H8NH2, H2NC41-ta NH2, H2NC5
HION+-[2, Me2 NC2H4NMe2
, Me2NC3H6N Me2C2H40H These are preferred specific examples of the base precursor, but are not limited to these.

Examples of compounds whose acid moieties are thought to decarboxylate and release bases include the following:

Examples of trichloroacetic acid derivatives include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, and the like.

Other British Patent No. 998,945, U.S. Patent No. 3,2
The base precursors described in No. 20,846, JP-A No. 50-2225, etc. can be used.

Other than trichloroacetic acid, U.S. Patent No. 4.088
, 2-carpoxylboxamide derivatives described in No. 496,
Examples include the α-sulfonylacetate conductor described in U.S. Pat. No. 4,06,420, and the salt of a propiolic acid derivative and a base described in JP-A-59-180537.
In addition to organic bases, salts containing alkali metals and alkaline earth metals as base components are also effective, as disclosed in Japanese Patent Application Laid-Open No. 59-195.
It is described in No. 237.

Precursors other than those mentioned above include hydroxamic carbamates described in Japanese Patent Application No. 58-43860 using Rossen rearrangement, and Japanese Patent Application Laid-open No. 168440-1987 which generates nitriles.
Aldoxime carbamates described in the above are effective.

Research Disclosure Magazine May 1977 Issue 1
Amine imides described in No. 5776, JP-A-50-226
Aldonamides described in Publication No. 25 are preferably used because they decompose at high temperatures to produce bases.

These bases or base precursors can be used in a wide variety of ways. A useful range is 50% by weight or less, more preferably 0.01% to 40% by weight of the coated bellows of the photosensitive material.

Silver halide that can be used in the present invention is disclosed in Japanese Patent Application No. 59-21
Silver halide produced according to the method described on pages 25 to 29 of No. 3978, containing the additives described therein, and having the properties described therein can be used.

Silver halide emulsions may be used as they are after ripening, but they are 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.

The silver halide emulsion used in the present invention may mainly be of the surface latent image type in which a latent image is formed on the surface of the grains, or may be of the internal latent image type in which the latent image is formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/rn'' in terms of silver.

In the present invention, it is desirable to use an organic metal salt relatively stable to light, particularly an organic silver salt, as an oxidizing agent together with the photosensitive silver halide.

For details on organic silver salts that can be used, see Japanese Patent Application No. 59-2.
No. 13978, pages 30-34.

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

Regarding these pigments and their details, please refer to the patent application filed in 1983.
-213978, pages 34 to 38.

In the present invention, a reducing agent is included in the photosensitive material. As the reducing agent, those known in the art and the reducing dye-providing substances described below are preferred.

As a specific example of the reducing agent used in the present invention, Japanese Patent Application No. 59
-209563, pages 61 to 64 can be used.

In the present invention, a compound that produces or releases a mobile (diffusible) dye in response to or inversely to the reduction of photosensitive silver halide to silver under high temperature conditions. , that is, it can contain a dye-providing substance. Next, the dye-providing 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 are available from, for example, T.H. James (T, tl, J
ames), The theory of the photographic process (The theory of the photographic process)
(photographic process) 4th edition (
4Lh E'd,) pages 291-334, and 35
4-361 pages, Makoto Kikuchi, “Photochemistry” 4th edition (
(Kyoritsu Shuppan) pages 284-295.

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 are given in Research Disclosure magazine, May 1978 issue, pages 54-58 (RD-169
66) etc.

Furthermore, azo dyes used in 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 disclosed in U.S. Pat. No. 4,235,957.
No., Research Disclosure magazine, April 1976 issue, pages 30-32 (RD-14433).

Also, U.S. Patent No. 3.985,565, U.S. Patent No. 4.022
, No. 617, etc., can also be mentioned as an example of the dye-donating substance.

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

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

(Dye - 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 having a property that causes a difference in diffusivity between it and 1-Y, n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different. You can.

As a specific example of the dye-donating substance represented by the general formula [L1], for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in U.S. Patent No. 3,134,764.
No. 3, No. 362.819, No. 3,597,20
No. 0, No. 3,544,545, No. 3゜482.9
It is described in No. 72, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was disclosed in JP-A-51-
63618 etc., substances that release diffusible dyes through an intramolecular rewinding reaction between isoxacilones were disclosed in Japanese Patent Application Laid-open No. 4.
No. 9-111628, 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.

Another method is to make the dye-releasing compound in an oxidized form without dye-releasing ability in advance and coexist with a reducing agent or its precursor, and after development, reduce it with the reducing agent that remains unoxidized. A system for releasing a diffusible dye has also been devised, and specific examples of dye-donating substances used therein are disclosed in JP-A-53-110827 and JP-A-54-13.
No. 0927, No. 56-164342, No. 53-355
It is described in No. 33.

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, Special Publication 1973-39
No. 165, U.S. Pat. No. 3,443,940, etc., and U.S. Pat. No. 3, U.S. Pat. , No. 227,550, etc.

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, dye-donating compounds that do not require a developer and have reducing properties themselves have been devised.

Representative examples can be found in the following documents. Definitions in the general formula are described in each literature.

For example, U.S. Pat. No. 3,928,312;
No. 053,312, No. 4,005゜428, No. 4
, No. 336, 322, JP-A No. 59-65839, No. 5
No. 9-69839, No. 53-3819, No. 51-10
No. 4343, Research Disclosure Magazine 174
No. 65, U.S. Patent No. 3,725,062, U.S. Patent No. 3,7
No. 28,113, No. 3,443゜939, JP-A-5
Any of the various dye-providing substances described in Japanese Patent No. 8-116537 can be used in the present invention.

Specific examples of the dye-donating substance that can be used in the present invention include the compounds described on pages 60 to 91 of the aforementioned JP-A-59-84238. Compounds (1) to (3) described (to)
~(13), (16) ~(19), (28) ~(30)
, (33), (35), (38) to (40), (42
) to (64) are preferred. In addition, the patent application No. 59-246
Compounds described on pages 82 and 83 of No. 468 are also useful.

The dye-providing substances and photographic additives used in the present invention are:
Four layers can be incorporated into the photosensitive material layer by known methods such as those described in U.S. Pat. No. 2,322,027.

In that case, the above-mentioned high boiling point organic solvents and low boiling point organic solvents can be used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using polymers described in No. 3 can be used. Furthermore, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid.

In the present invention, an image formation accelerator can be used in the light-sensitive material. 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, and photosensitive material layers. It has the function of promoting the movement of the dye from the dye fixing layer to the dye fixing layer, and from a physicochemical function, it has the function of promoting the movement of the dye from the above-mentioned base or base precursor, nucleophilic compound, oil, hot solvent, surfactant, silver or silver ion. It is classified as a compound that has interactions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

For details of these, see Japanese Patent Application No. 59-213978 6.
It is described on pages 7-71.

Further, in the present invention, a compound that activates the development and stabilizes the image can be used in the photosensitive material.

For specific compounds that are preferably used, see Japanese Patent Application No. 1983.
-213978, pages 73-74.

In the present invention, the photosensitive material may contain an image toning agent if necessary. Specific examples of effective toning agents are described in Japanese Patent Application No. 59-213978, pages 74-75.

The binders used in the photosensitive material of the present invention may be contained alone or in combination. A hydrophilic binder can be used for this binder. Typical single-layer wood-philic binders are transparent or translucent hydrophilic binders, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, and polyvinyl Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as pyrrolidone and acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others.

In the present invention, the binder is applied in an amount of 20 g or less per bag, preferably 10 g or less, more preferably 7 g or less.
g or less is appropriate.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 g of binder to 1 g of solvent or less, preferably 0.
A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other binder layer.

Specific examples and specific compound examples include those described in Japanese Patent Application No. 59-213978 @ pages 76 to 77, and these can be used alone or in combination.

The supports used in the light-sensitive materials and optionally used dye-fixing materials of the present invention are those that can withstand processing temperatures. As a general support,
Not only glass, paper, metal and their analogues are used, but also Japanese Patent Application No. 59-213978, page 77~
Those listed as supports on page 78 can be used.

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.

In a system in which the transfer aid is externally supplied, water or a basic aqueous solution containing caustic soda, caustic potash, an inorganic alkali metal salt, and an organic base is used as the dye transfer aid. As these bases, those described in the section of the image formation accelerator can be used. Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used. The dye transfer aid may be used in a method in which the dye fixing/fixing material or the light-sensitive material or both are wetted with the transfer aid.

When the light-sensitive material used in the present invention contains a colored dye-donating substance, it is not so necessary to further contain an irradiation-preventing substance, an anti-halation substance, or various dyes. However, filter dyes, absorbent substances, etc. described in the literature exemplified on page 80 of Japanese Patent Application No. 59-213978 can be included.

The photosensitive material used in the present invention may contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an A
It can contain an H layer, a release layer, etc. For various additives, see Research Disclosure Magazine Vol.

170. Additives described in No. 17029, June 1978, such as plasticizers, sharpness-improving dyes, A
Additives include H dyes, sensitizing dyes, matting agents, surfactants, optical brighteners, and anti-fading agents.

The photographic element of the present invention is comprised of a light-sensitive element that forms or releases a dye upon heat development and, optionally, 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. There are two types of coatings: those that are coated on the same support and those that are coated on the same support.

The relationship between the dye element and the dye fixing element, the relationship with the support,
Regarding the relationship with the white reflective layer, the relationship described on pages 81 to 82 of Japanese Patent Application No. 59-213978 can also be applied to the present application.

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, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. As a preferable embodiment, for example, Japanese Patent Application No. 59-213978, No. 8
The description is on the 5th line to the 2nd line from the bottom of page 2.

Another typical embodiment in which a photosensitive element and a dye fixing element are coated on the same support includes, for example, Japanese Patent Application Laid-Open No. 56-67840.
Canadian Patent No. 674°082, U.S. Patent No. 3,7
30,718, in which part or all of the light-sensitive element is peeled off from the 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 in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, the photosensitive element used in the present invention comprises at least three layers of halogen, each sensitive to a different spectral region. It is necessary to have a silver oxide emulsion layer.

Typical combinations of at least three photosensitive silver halide emulsion layers sensitive to different spectral regions include Japanese Patent Application No. 59-213978, 83-84.
There is something written on page 7 line.

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 hydrophilic colloid layer adjacent to each emulsion layer is
It is necessary to contain at least one of the compounds listed from line 7 below page 82 to line 8 of page 85 of the specification of No. 3978.

In addition to the above-mentioned layers, the photosensitive material used in the present invention may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matting agent layer, if necessary.

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

Further, the intermediate layer may contain a reducing agent, a UV absorber, and a white pigment such as TiO2 to prevent color mixing. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing 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.

The layer structure of the dye fixing element, the binder, additives, and mordant addition location are as described in Japanese Patent Application No. 59-213978, No. 8.
The descriptions from page 6, line 10 to page 88, line 10 and the patent specifications described therein can also be applied to the present application.

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 migration, a hydrophilic thermal solvent, an antifade agent to prevent color mixing of the dyes, a UV absorber, a dimensional stability Dispersed vinyl compound for increasing
A fluorescent whitening agent or the like may also be included.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. Specifically, the binders mentioned above for the photosensitive materials are used.

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 these methods are disclosed in Japanese Patent Application No. 59-213978, No. 8.
Those described on page 9, lines 2 to 13 can be used according to the method and layer structure described therein according to the distinctions described therein.

Regarding the mutual positional relationship between the heat generating element and the photosensitive element, the same as described in the fifth line from the bottom of page 89 can be applied.

The image receiving layer in the present invention includes a dye fixing layer used in heat-developable color light-sensitive materials, and can be arbitrarily selected from commonly used mordants, among which polymer mordants are particularly preferred. Here, the polymer mordant includes 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.

For specific examples, please refer to Japanese Patent Application No. 59-213978 90.
It is described in the literature illustrated on pages 1 to 91.

In the present invention, the method described on pages 91 to 92 of the specification of the above-mentioned application number can be used as a coating method for the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, and other layers.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used,
For example, the light source described on page 92 of Japanese Patent Application No. 59-213978 can be used.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 10°C to about 180°C. The heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but it is particularly preferably up to a temperature about 10° C. lower than the temperature in the heat development step. 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.

Furthermore, as detailed in Japanese Patent Application No. 59-218443, a method in which development and transfer are carried out simultaneously or consecutively is also useful. In this method, the above-mentioned image formation accelerator and/or dye transfer aid may be included in the dye fixing material, the light-sensitive material, or both in advance, or may be supplied from the outside. good.

In this system in which development and transfer are performed simultaneously or continuously, the heating temperature is preferably 60° C. or higher and lower than the boiling point of the solvent used for transfer. For example, if the transfer solvent is water, 6
The temperature is preferably 0°C or higher and 100°C or lower.

A dye transfer aid (for example, water) is added between the photosensitive layer of a heat-developable 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.

As a method for applying a dye transfer aid to a photosensitive layer or a dye fixing layer, for example, Japanese Patent Application No. 59-213978 No. 93
There are methods described in lines 6 from the bottom of the page to lines 2 from the bottom of page 94.

The heating means in the transfer process is disclosed in Japanese Patent Application No. 59-21397.
There is a means described in No. 8, page 94, last line to page 95, line 10.

Alternatively, a layer of an electrically conductive material such as graphite, carbon black, or metal may be applied to the dye-fixing material in an overlapping manner, and an electric current may be passed through this electrically conductive layer to heat it directly.

The heating temperature applied in the transfer step can be in the range from the temperature in the heat development step to room temperature, but in particular 6
The temperature is preferably 0° C. or more and 10° C. or more lower than the temperature in the heat development step.

The pressure conditions and method of applying pressure when overlapping and bringing the heat-developable photosensitive material and the dye-fixing material into close contact are described in a patent application published in 1983.
The method described on page 96 of No. 213978 can be applied.

■Specific Effects of the Invention According to the present invention, since it contains the compound represented by the general formula (I), it is possible to stop the development at the time of proper development without reducing the image density. A photosensitive material is obtained. Moreover, high-quality images can be formed without adverse effects such as environmental pollution.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in more detail.

EXAMPLE A multilayer color photosensitive material was prepared by coating the following first layer (lowest layer) to sixth layer (fi upper layer) on a polyethylene terephthalate film support.

First, we will describe how to make a hensitriazole silver emulsion.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3000 mji4 of water. This solution was kept at 40°C and stirred. Add 17g of silver nitrate to this solution.
was dissolved in 100rnJZ of water and added over 2 minutes.

The pi of this benzotriazole silver emulsion was adjusted, precipitated, and excess salt was removed. Thereafter, the ptl was adjusted to 6.3 to obtain a benzotriazole silver emulsion with a yield of 400 g.

Next, a method for preparing a silver halide emulsion for the fifth layer will be described.

A well-stirred aqueous gelatin solution (20 g of gelatin and ammonia dissolved in 10,100 O of water and kept warm at 50°C) was mixed with 1,000 m of an aqueous solution containing potassium iodide and potassium bromide and an aqueous solution of silver nitrate (100,100 O of water).
(1 mole of silver nitrate dissolved in O) and PAg
was added while keeping it constant. In this way, a monodispersed silver iodobromide octahedral emulsion (5 mol % of iodine) with an average grain size of 0.5 μm was prepared.

After washing with water and desalting, 5 mg of chloroauric acid (tetrahydrate) and 2 mg of sodium thiosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion was 1.0 kg.

Next, I will talk about how to make the emulsion for the third layer. A well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride in 100,100 O of water kept at 75°C) was mixed with 600 mM of an aqueous solution containing sodium chloride and potassium bromide and an aqueous solution of silver nitrate (600 mfi of water with 0 silver nitrate). 0.59 mol dissolved) and the following dye solution (I) were simultaneously added at equal flow rates over a period of 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol %) was prepared, in which a dye having an average grain size of 0.35 μm was adsorbed.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene were added to perform chemical sensitization at 60°C.

The yield of emulsion was 600g.

Next, the method for preparing the first layer emulsion will be described.

A well-stirred gelatin solution (1000 ml of water)
' Contains 20g of gelatin and 3g of sodium chloride 75
600 ml of an aqueous solution containing sodium chloride and potassium bromide (kept at
0.59 mol of silver nitrate dissolved in 00 mL) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene were added to perform chemical sensitization at 60°C.

The yield of emulsion was 600g.

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

Weigh out 5 g of yellow dye-donating substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 10 g of triiso-nonyl phosphate, add 30 ml of ethyl acetate, 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, use a homogenizer for 10 minutes,
It was dispersed. This separated liquid is called a dispersion of a yellow dye-providing substance.

A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except that the magenta dye-providing substance (B) was used and 7.5 g of tricresyl phosphate was used as a high-boiling solvent.

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

= H-〇(C) Next, a method for preparing a gelatin dispersion of the compound (4) of the present invention will be described.

10 g of the compound (4) of the present invention, 0.5 of the following surfactant
g to 100 g of a 1% aqueous gelatin solution, and milled to approximately 0.0 g.
Milled for 10 minutes with a glass bead with an average particle size of 6 mm+. The glass peas were separated by filtration to obtain a gelatin dispersion of compound (4) of the present invention.

Surfactant CH2CC00CH2O-nNa0
3 In SS-CHCooCHog-n photosensitive material 1, the compound (1) of the present invention was substituted for the compound (4) of the present invention.
, and (5) were used in exactly the same manner except that they were used as photosensitive material (■).

■Created.

In addition, in the photosensitive material process, materials using the following compound (a) in place of the compound (4) of the present invention and materials without the addition of the compound (4) of the present invention were also prepared, and in order, photosensitive materials IV, It was set to V.

Compound (a) Next, we will discuss how to make the dye fixing material.

Poly(methyl acrylate-N, N, N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) was dissolved in 200 IIIL of water and treated with 10% lime. It was uniformly mixed with 100 g of gelatin. This mixed solution was uniformly applied to a wet film thickness of 90 μI on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material having a mordant layer.

The multilayered color photosensitive material IV was exposed to light for 1 second at 2000 lux using a tungsten light bulb through a three-color separation filter of B, G, and H whose density was continuously changed. Thereafter, the film was heated uniformly for 15 seconds on a heat block heated to 150° C. or 153° C. with the film surface open.

Next, 20rsJJ per 1 m2 on the membrane side of the dye fixing material,
After supplying water, the heat-treated photosensitive coatings were stacked on a fixing material so that the film surfaces were in contact with each other.
After heating on a beat block at 80°C for 6 seconds, the dye-fixing material is peeled off from the light-sensitive material, and B and G appear on the fixing material.
, R color images were obtained corresponding to the three-color separation filters of yellow (Y), magenta (M), and cyan (C), respectively. The maximum density and minimum density of each color were measured using a Macbeth reflection densitometer (RD519).

Roughly speaking, each photosensitive material was similarly heated at 153° C. for 60 seconds, and the remaining amount of the compound used was analyzed to determine the volatilization rate.

Volatilization rate (%) = -x 100 a: Addition amount in photosensitive material (heating chamber) X: Remaining amount in photosensitive material (after heating) These results are shown in Table 1.

Table 1 shows that the heat-developable photosensitive material using the compound of the present invention shows little variation in both maximum density and minimum density even when the development temperature is increased by 3°C, has an excellent temperature compensation effect, and produces high-quality images. It can be seen that the following can be obtained.

Since the photosensitive material of the present invention has a low failure rate even when heated under severe conditions, it can be said that such an effect is produced without causing environmental pollution.

Therefore, the effects of the present invention are obvious.

Applicant: Fuji Photo Film Co., Ltd. "child.

Claims (1)

[Scope of Claims] A heat-developable photosensitive material comprising at least a photosensitive silver halide emulsion and a compound represented by the following general formula (I) on a support. General formula (I) R_1-O-Ar_1-L-Ar_2-O-R_2 {In the above general formula (I), R_1 and R_2 each have a ▲ mathematical formula, chemical formula, table, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R_3 and R_4 each represent a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, or a heterocyclic residue) ). Ar_1 and Ar_2 each represent a substituted or unsubstituted arylene group. L represents a substituted or unsubstituted divalent linking group or a simple bond. }