JPS61261737A - Heat developing color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the colored image having a low min. concn. and a high max. concn. by incorporating a specific compd. to the title material, thereby improving a photosensitivity and restraining a fog-generation, while accelerating a development. CONSTITUTION:The title material is prepared by providing a photosensitive silver halide, a binder and a substance affording a coloring matter by forming or releasing a movable dyestuff accommodating or adversely accommodating with a reaction of reducing the photosensitive silver halide to a metal silver at the high temp. as essential components on a substrate, and by incorporating at least one kind of the compd. shown by the formula R1-S-R2 wherein R1 and R2 are each (unsubstd.) substd. aliphatic, aromatic or heterocyclic group, R1 and R2 together with S atom may be formed a 5-7 membered ring to the title material. The prescribed compd. may be preferably added to the photosensitive layer. However, the compd. may be added to the color fixing element in the state of contacting the color fixing element with the photosensitive element in the heat development. The prescribed photosensitive material may be developed for a short period, and the obtd. colored image gives a vivid image, and the stable development may be obtd. even if the developing condi tion is changed.

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a new heat-developable color photosensitive material that forms a dye image by heating. (Prior art) Photography using silver halide has been the most widely used method since it has excellent photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. I've been exposed to it. In recent years, the image forming process for photosensitive materials using silver halide has been changed from the conventional wet processing using a developer at room temperature to a thermal development process using heating, etc., which allows images to be created easily and quickly. Techniques have been developed to enable this. Many methods have been proposed for obtaining color images by heat development. Regarding a method of forming a p-color image by combining an oxidized developer and a coupler, U.S. Pat. U.S. Pat. No. 3,761,4270 discloses that p-aminophenol reducing agents are used in Ilgy Patent No. 802,51.
No. 9 and Research Disclosure Magazine 1975 9
Month number 31, rope, 32 is positive, Bt, sulfonamide phenol reducing agent, and US Patent No. 4,
No. 021,240 proposes a combination of a hornamine cyenol starting agent and a 4-equivalent carboxylic acid. :・・・1.Papa□ Research Disclosure Magazine, May 1978 issue 5 also describes a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development.
4 to 58 are described in Posi RD-16966. ) A positive color image is created using the photosensitive silver dye bleaching method. 'ilffltBJmKzzi
il:, *, =, tit'・')"j-ff17.,
Isk-ja magazine April 1976 issue 30
．． ~32;'("1 page (RD-1443
3), December 1976 issue of the same magazine, 1 So□・14-1. -, -di(RD-15□2
7), U.S. Patent No. 1 □l 4,235,9
Useful dyes and bleaching methods are listed in No. 57, etc.
, is listed. ! , l: Also, regarding the method of forming a color image using the icosate dye, for example, U.S. Pat. No. 3,985,565
No.°'1: Described in No. 4,022,617. However, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the drawbacks of only high capri and low density. In order to improve these drawbacks, an image forming method using silver halide has been proposed in which a mobile element is formed in the form of an image and this is transferred to a dye fixing layer. (Unexamined Japanese Patent Publications No. 58-58543, No. 58-79247, No. 5
8-149046, 58-149047). (Problems to be Solved by the Invention) However, conventional heat-developable color photo-recording materials have low sensitivity, insufficient development speed, and although the maximum density of images is not sufficiently high. Even if you try to speed up the development speed or increase the maximum density by changing the development conditions such as heating temperature and time during development, you will not be able to obtain a sufficiently high maximum density, and the minimum density and υ [J fog will also increase. There was a problem. In addition, in order to obtain stable and good images, the developing conditions must be set constant, and even when the maximum developing conditions fluctuate,
There was a problem that the developability became unstable. Therefore, an object of the present invention is to provide a photothermographic material that can increase sensitivity, suppress fog while promoting development, and provide a dye image with a low minimum density and a high maximum density. It is in. Another object of the present invention containing this compound is to provide a heat-developable photosensitive material with small fluctuations in developability even when the development temperature or time changes, that is, the developability is stable. There is a particular thing. (Means for Solving the Problems) The problem is that when the support is coated with at least photosensitive silver halide and a binder, when the photosensitive silver halide is reduced to silver under high temperature conditions, there is no need for a support that supports this reaction. A heat-developable color light-sensitive material having a dye-providing substance that generates or releases a mobile dye in an inverse manner.
By containing at least one compound represented by formula fI), the above object can be achieved. ■ ,, -4E(Tl'',';l R-8-R・゛(, in the formula,
R□, R2 represent a substituted or unsubstituted aliphatic group, aromatic group or heterocyclic group, and R1 and R2 together with S represent 5
A seven-membered ring may be formed. Examples of the substituted or unsubstituted aliphatic group or aromatic group include an alkyl group (preferably having 1 to 22 carbon atoms), a cycloalkyl group (e.g. cyclohexyl group), and an alkenyl group (preferably having 1 to 22 carbon atoms). ), alkynyl group (preferably carbon number 1-
22), aralkyl groups (eg, phenyl, phenylethyl, tolbenzyl, naphthylmethyl, etc.), and aryl groups (eg, phenyl, naphthyl, todecylphenyl, etc.). The aliphatic groups of R1 and R2 may be linear or branched. The heterocyclic group is preferably a 5- to 6-membered ring containing at least one of nitrogen, oxygen, or sulfur atoms as a heteroatom. It may also have a fused ring. Specific examples thereof include imidazole ring, pyrazole ring, thiazole ring, thiadiazole ring, triazole ring, indazole ring, (zuimidazole ring, hanzutriazole ring, etc.) These aliphatic groups, aromatic groups or heterocycles Examples of the substituent group include halogen atoms (e.g. chlorine, bromine,
fluorine, etc.), -CN, -NRR', C0OR. -CONRR', -NHCOR, -NH8O2R, -
8○2NRR', -NO3゜-OH, -8-R, -8
Examples include O3M, -0-R, -8o2R, -8OR, and the like. However, R and R' here represent a hydrogen atom, an alkyl group (preferably having 1 to 22 carbon atoms), an aryl group (preferably substituted or unsubstituted phenyl), an aralkyl group (preferably benzyl, (tolbenzyl, phenylethyl, naphthylmethyl, etc.), or a heterocycle (for example. M represents a hydrogen atom, an alkali metal ion or an ammonium ion. The aliphatic group of R1 and R2 is a carbon-free connecting element or a linking element. It may contain a group, preferably 10-2-3--
3O--8ONH--8ON'-CONH-+
21 2 + 2
\! Examples include -coN<, -COO-, -NR-, and the like. Such R1. General formula with R2 (
Compounds of Il include the following general formulas [TA], [T-
The value expressed by B) is θ1. General formula rT-1 Q-((CH2)r-CH2-8-(CH2) 2-X
' -(R)p-(CH2) 2-(R' ), -8-
CH2-(CH2)rn-Z/). General formula ['I-B) Q, -(CT(2)m-CH2-8-(CH2)n-8
-CI(2-(CH2)r-Z' where r, m: integer 0 to 4 n: integer 1 to 4 p, q: integer O to 3 X': oxygen atom, sulfur atom, ○ 0O 11Il 1l -CNH-, -C-, -C-0- R, R': Ethylene oxide, z': Qp(//, -0OR// (R//
: hydrogen atom or alkyl group having 1 to 5 carbon atoms), -CNH2, and Q and X' represent a substituent represented by X', and can also be combined to form a cyclic compound. Specific examples of compounds represented by general formula (T) are shown below using structural formulas. (1) HO-CH2-CH2-CH2-8-CH2
-C12-OH(21HO-CH, , -CH2-8-
CH2-CH2-3-CH2-CH2-OH (3)
HO-CH2-CH2-CH2-8-CH2-CH2-
3-CH2-CH2-CH2-OH (4) HO-CH2-CH2-8-CT(2-CH2-
8-CH2-CH2-8--CH2-CH2-OH (5) Na03S-CH2-CH2-CH2-8-CH
2-CH2-8-C) T2-C! (2-CH2-8○3
Na -CH2-,OH (force HOOC-CH-8-CH-CH-8-CH2
-COOHf8j H2NC0-CH2-CH2-8
-CH2-CH2-8-CH2-C12C0NH2 (10) c) -CH2-8-CH2-CH2-OHf
ll) C1□H25-8-C42H2゜f12I
C, 8H37-8-C1□H2゜(13+C mowing CH
2-IJ-C4T(9(.)NH2(251HO-CH2-CH2-8-CH2-CH2-
OH(29) HO-CH2-CH2-8-CH2-
In the image forming system using the Co-0-CH3 photothermographic material, both a photosensitive element alone and a combination of a photosensitive element and a dye fixing element are applied. That is, the heat-developable color photosensitive material of the present invention may consist only of a photosensitive element or may further include a dye fixing element. The photosensitive element of the present invention comprises on a support at least a photosensitive silver halide, a binder, at least one compound of general formula (I), and a movable dye released or formed upon heating to form a color image. Contains a dye-donating substance. In this case, the dye-donating substance functions as a reducing agent!・, ′- may exist.・, # -$ J"("4"8"fd
m 5'e N K t<°2-2') is preferable, but a form is adopted in which the dye fixing element is present in contact with the photosensitive layer '1 1, l element at the time of thermal development. □If it is present, it may be added to the dye fixing element.ゞ ゝ3 ・: Here, the photosensitive layer means a heat-developable photosensitive element or a photosensitive photographic layer, which has at least one silver halide emulsion layer, an intermediate layer, It means a laminated colloidal layer which may contain a protective layer etc., and when there is a non-photosensitive pack layer on the side opposite to the support, it means "1".j of general formula (I) of the present invention. When a compound is added to the photosensitive layer, the amount added is preferably 0.01 to 100 mol, preferably 0.05 to 50 mol, based on the total amount of coated silver (number of moles). , particularly preferably 0
1 to J:: 20 mol. Also, when added to the dye fixing element, it is added to the photosensitive layer. When using, double the amount and add -c. I can do something. In addition to the compound of the general formula (Il), it is preferable to use at least one compound of the following general formula (m or (ITT)). The heterocycle formed by Z in the general formula is preferably a 5-, 6- or 7-membered heterocycle, and these have a fused ring. or may have a heteroatom other than the N atom.General formula (among the compounds marked with the mark, the following general formula (
Compounds represented by TI-1) to (IT-9) are preferred. (TI-3) (TI-4) (TT-5
) (IT-6) (IT-7)
(IT-s) (1'r-9) In the formula, R1, R2, R3, and R4 are each a hydrogen atom, an alkyl group (preferably having 1 to 22 carbon atoms), an aralgyl group (e.g. Eva, phenylethyl group, tolbenzyl group,
naphthylmethyl group, etc.), alkenyl group (preferably 1 to 22 carbon atoms), alkoxy group (preferably 1 to 22 carbon atoms),
22), IJ-l group (preferably L<, substituted or unsubstituted phenyl group), -NRR', -CO○R", -CON
'RR', -NH8O2R. -8o NRR', -NO2, halogen source]', -c
N or -OH (where R and R' are hydrogen atoms, alkyl groups (1 to 22 carbon atoms), or -
R represents a group (preferably a substituted or unsubstituted phenyl group, etc.), an aralkyl group (preferably a benzyl group, a phenylethyl group, a tolu group, a naphthylmethyl group, etc.),
" is an alkyl group (preferably 1 to 22 carbon atoms), an aryl group (preferably a substituted or unsubstituted phenyl group), an aralkyl group (preferably a benzyl group, a phenylethyl group, a tolynzyl group, a naphthylmethyl group) ). In the general formula (IT-9), R□ and R2 may be combined with each other to form an aliphatic ring or an aromatic ring. R5 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms. Motomada-3
represents R1'L. (The RILL group represents a hydrogen atom, an alkyl, aryl or aralkyl group). R6 is a hydrogen atom or an alkyl group, and R7 is a hydrogen atom, an alkyl group, or an aryl group. R8 represents an alkyl group, an aryl group, a benzyl group, or a pyridyl group. Among the above compounds, the compound represented by the general formula (IT-9) is particularly preferred, and among these, the compound represented by the following general formula (■-10) is even more preferred. (ff-10) In the formula, R9 and Rlo are the same as the above R1 and R2 General formula (D) B-3-H In the formula, B is -alkyl group, cycloalkyl group, alkenyl group, alkynyl group, Represents an aralkyl group, an aryl group, or a heterocyclic group. In B of the above general formula (III), [alkyl group J may be linear or branched. Examples of alkyl groups include butyl group, isobutyl group, cyclohexyl group, heptyl group, octyl group, dodecyl group, and examples of substituents for substituted alkyl groups include alkoxy groups (such as methoxy groups), hydroxy group,
These include a cyano group, a norogen atom, and 9 sulfonamide groups. Examples of cycloalkyl groups include cyclo for methyl, cyclohexyl, decahyde-50 naphthyl, etc.; examples of alkenyl groups include pro-nyl, isozolo for nyl,
Examples of alkynyl groups such as styryl group include ethynyl group and phenylethynyl group. Examples of aryl groups include phenyl group and naphthyl group, and examples of substituents for substituted aryl groups include alkyl groups (methyl group, dodecyl group, etc.), cyano group, nitro group,
Amine group, acylamino group, 9 sulfonamide groups (including aliphatic, aromatic, or heterocyclic groups), alkoxy group, aryloxy group, alkoxycarbonyl group, ureido 9 group, carbamoyl group , acyloxy group, heterocyclic group (5- to 6-membered ring, preferably nitrogen-containing heterocycle), alkylsulfonyl group, carboxylic acid group, sulfonic acid group, sulfamoyl group, halogen atom (
fluorine, bromine, chlorine, iodine), etc. These substituents may be further substituted. There may be two or more substituents as illustrated above. These substituents are also suitable for the following groups, I
Can be used.゛・ Examples of aralkyl groups include henzyl group and fe・)) netyl group. The heterocyclic group is preferably a 5- to 6-membered ring containing at least a nitrogen, oxygen, or sulfur atom as a heteroatom. Specific examples include furan ring residues, thiophene ring residues, pyridine ring residues, quinoline ring residues, thiazole ring residues, and nzothiazole ring residues. Thus, the heterocyclic group may be a single ring or a fused ring thereof. Among the compounds of general formula (m), the following general formula (m-1)
Compounds represented by are preferred. General formula (m-1) 1 In the formula, Q is an oxygen atom, i, a t7 atom, a nitrogen atom, or -NR- (Rn is a hydrogen atom, each substituted or unsubstituted alkyl group (preferably 1 to 5 carbon atoms) i
1. 7,707/L=-11'"g
(f"1'"・°-1xyl group), unsaturated alkyl group (preferably 1 to 18 carbon atoms), aryl group (preferably substituted or unsubstituted phenyl group), aranoyl group

[-Kyl group (preferably tL< represents a benzyl group, phenylethyl group, tolbenzyl group, naphthylmethyl group). ). Z' represents an atomic group necessary to form a 5- or 6-membered heterocycle together with -Q-C=N-. This heterocycle may have a fused ring. Among the compounds represented by the general formula (m'-1), the compounds represented by the following general formula (TII-2) are preferred. (III-2) In the formula, R□ and R□2 are R of general formula (IT-9)
Yo. It has the same meaning as R, and Q has the same meaning as Q in general formula (In'-1), but is preferably -NH-. Specific examples of compounds represented by general formula (10 or general formula (III)) are listed below. ' (1) (
2+ (31' (4)
(51 (61) □・,・・1 t Pa barrel (7) (8) (9), 11
．． ;Ql H(+21(+5)
(16) Examples of compounds of the general formula (TIT) are listed below in terms of structural formulas. (4 wings (50) Nori GFQ side (60):,
, 4 +611 (62(
63) (64) (6 most
(66) (67) (68)
(6!1it(” 'l
(71ff1) ff3σ31
σ4) 0ff6)
ση general formula (II) or (T
II) (L compound) is preferably 0 with respect to the total coated silver amount.
01 to 100 molar ratio, further 001 to 20 molar ratio, especially 0
．． It is used in a range of 1 to 10 moles. When added to a dye fixing element, it can be added up to twice the above amount. Compounds of general formula (IT) or (Tff) are compounds of general formula (IT) or (Tff).
It may be added to the same layer as the Il compound, or it may be added to separate layers. Preferably, the compound of general formula (II) or (m) is added to one or more silver halide emulsion layers together with the compound of general formula (I). , ; General formula (T)・(11)・(m) (
7) The compound is a solid compound, and 1 is usually a solvent (preferably 1 is water, 1 is methanol,
Dissolved in ethanol, dimethylformamide 9, methyl cellulose, etc.), emulsion-like, 11
It is added during manufacturing and coating solution preparation. When using a water-soluble piper, it can be added by dissolving it in a water-immiscible organic solvent, oil, etc. and emulsifying and dispersing it. ,j O, 1゜7kaah, I, □, 67,. A74
．． -1, r: , 1i, I Silver chloride, silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. )'l', :,,""'l,
<% It has a multilayered structure with different compositions on the surface and inside. Even if the halogen composition within the particles is uniform...
″:Moru (JP-A No. 57″″ 154232, No. 58-: Ko IQ3533, No. 59-4
No. 8755, No. 59-52237, No. 1, U.S. Pat. No. 4,433,048 and European Patent No., Ding:,,,H (1o 0.984). In addition, if the thickness of the particles is 0.5 μm or more, ,. 6□. A. Tabular grains with a 7.2° ratio of 5 or more (U.S. Patent No. 4,414,31.0, U.S. Patent No. 443 to 499, OLS No. 3.241,646AI, etc.)
, or monodispersed emulsions with nearly uniform particle size distribution (JP-A-57-178235, JP-A No. 58-100846,
No. 58-14829, International Publication No. 83102338A1
No. 64,412A3 and European Patent No. 83,37
7AI, etc.) may also be used in the present invention. Two or more types of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing two or more types of monodispersed emulsions having different grain sites 9. The grain size of the silver halide used in the present invention preferably has an average grain size of 0.001 μm to 10/Im, more preferably 0.001 μm to 5 μm. These silver halide emulsions may be prepared by any of the acid method, neutral method, or ammonia method, and the reaction method of the soluble silver salt and soluble halide salt may be one-sided mixing method, simultaneous mixing method, or any of these methods. Any combination of these may be used. Back-mixing method where particles are formed under silver ion excess, or pAg
It is also possible to adopt the Chondral double jet method with -constant Kff. However, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Laid-Open Nos. 55-1.42329, 55-158124, U.S. Pat. No.:'(650,
No. 757, etc.). Epitaxially bonded halogenated scissor particles can also be used (JP-A-56-16124, U.S. Pat.
, No. 094, 684). In the present invention, an organic silver salt oxidizing agent as described below can be used in combination, but when silver halide is used alone without being used in combination, X-rays and ξ turns of silver iodide crystals may be observed. It is preferable to use silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Such a silver salt can be obtained by adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding potassium iodide to obtain silver iodobromide having the above characteristics. In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, and Japanese Patent Publication No. 47-1
The organic thioether derivatives described in No. 1386 and the sulfur-containing compounds described in JP-A-53-144319 can be used. In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present. Further, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (m, TV) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used. The silver halide emulsion may be free of soluble salts after precipitation or physical ripening, and thus can be subjected to Nudel water washing or precipitation methods. Although the silver halide emulsion may be used as it is, it is usually used after being chemically sensitized. For emulsions using conventional photosensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-1.26526, JP-A-58-215644).
. The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used. Internal latent image emulsions suitable for this purpose are disclosed in US Pat.
It is written in the number etc. Preferred nucleating agents for combination in the present invention include U.S. Pat. No. 3,22''1552;
Same No. 4,245,037, Same No. 4.255,51.1
No. 4.266031, No. 1, 27 to 364 and OLS No. 2. It is described in fi35,316 etc. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 to 1 oy7 in terms of silver. In the present invention, an organic metal base which is relatively stable to light can be used together with the photosensitive silver halide as an oxidizing agent. In this case, it is necessary that the photosensitive silver halide and the organic metal salt be in contact with each other or at a close distance. Among these metal salts, organic silver salts are particularly cleverly used. When an organic metal salt is used in combination in this way, the temperature of the photothermographic material is 80°C or higher, preferably 10°C.
When heated to a temperature of 0° C. or higher, the organometallic oxidizing agent is also considered to participate in redox using the silver halide latent image as a catalyst. Organic compounds that can be used to form the above organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, compounds having an acetylene group, and imino Examples include group-containing compounds. In addition, silver salts of compounds of the general formulas (JT) and (T) can be used. Examples of silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, and myristic acid. Acids, ) lumitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, lylic acid, oleic acid,
9. Derived from adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid, or camphoric acid. . 2゛pa. 6j153, a typical example is the silver salt derived. These o, 1, ゝ. Silver salts derived from the page atoms of fatty acids or hydroxyl acids can also be used, or carpone for fats with thioether groups can be used.゛□ Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 3.
5-dihydroxybenzoic acid, o-lm= or p-
', -, I 71 + /l/'El'! ,*”
・“-)po yv9.@$14”・11 to 7゛
” 7 ° “*,ra,*
p・ ” −′ ”−′cough, t5.8 ＃・ Axis □・
;: Tannic acid, phthalic acid, terephthalic acid, :: “・ Rutile acid, phenylacetic acid, pyromellitic acid type or substituted 3-ruboxymethyl-4-
Representative examples include silver salts derived from methyl-4-thiazo1, phosphorus-2-thione, and the like. Mercap;・Mori、＜is thio force゛′1
Examples of silver salts of compounds having a group include 3-゛) group F, -4-7''=#-
1,24-)su7zole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole,
2-mercaptobenzothiazole, S-alkylthioglycolic acid (alkyl group has 12 to 22 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearamyl, 5-carboxy-1-methyl-2
-Phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-L
24-1-Riazole etc. U.S. Pat. No. 4,123,27
Examples include silver salts derived from mercapto compounds described in No. 4. As a silver salt of a compound having an acetylene group, a patent application filed in 1982
Representative examples include silver salts of the compounds described in No. 193468, such as phenylacetylene silver. As a silver salt of a compound having an imino group,
3 (Incitriazole or its derivatives described in No. 1270 or No. 45-18416, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, halogen-substituted benzos such as 5-chloroincitriazole: 1. Cayaboio such as Azoya, etc. 7zo, riaci 7., triazoles, butylcarboimidobenzotri JP-A-1983-1
18639 (nitro is nzo) IJ azoles,
Sulfobenzotriazole, carboxybenzotriazole or a salt thereof described in JP-A No. 58-118638, or human 90x-inzotriazole, 1,24-) lyazole and IH-tetrazole described in U.S. Pat. No. 4.22Q709, 11. Representative examples include silver salts derived from carbazole, saccharin, imidazole, and derivatives thereof. Also described in RD17029 (June 1978), 1
″″4 silver *+, :x, f7! J7M9;
flJfx EO) @*JJ, outside 0 existence [)
metal salts, carboxylic acids having alkyl groups such as phenylpropiolic acid described in Japanese Patent Application No. 58-221535;
Silver salts of acid can also be used in the present invention. 1. i or more 0 organic silver salt is ・4-optical/゛O
0.01 to 10 mol, preferably 0.01 to 1 mol, of silver oxide can be used together. , 1.1゜□□84.Y5゜, I~10g/rl? is suitable. In the photosensitive element of the present invention, photosensitive silver halide is reduced to silver under high temperature conditions to obtain a dye image. In response to this reaction, or inversely, a mobile dye is generated.
□Or contains a releasing compound, ie, a dye-donating substance. Next, the dye-donating substance will be explained. Examples of dye-donating substances that can be used in the present invention include couplers that can react with reducing agents. This method using a coupler, in which an oxidized product of a reducing agent produced by a redox reaction between a silver salt and a reducing agent reacts with the coupler to form a dye, is described in numerous documents. Specific examples of reducing agents and couplers include:
For example, “The theo” by T. H. James.
ry of the photogr-apic p
rocess"4th, Ea 1291-334, pages 354-361, Makoto Kikuchi, 6 Photo Chemistry, 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 example of dye silver compound d: Research Disclosure Magazine, 1978, 5
It is described in the monthly issue, pages 54-58, (RD-16966), etc. Azo dyes used in the heat-developable silver dye bleaching method can also be cited as examples of dye-providing substances. Specific examples of azo dyes and bleaching methods are disclosed in U.S. Patent No. 4.2.
3Fx957, Research Disclosure Magazine, 1
April 976 issue, pages 30-32 (RD-14433
) etc. No. 3,985,565, U.S. Patent No. 4.022.
Leuco complexes, which are described in No. 617 and the like, can also be cited as examples of dye-donating substances. Another example of a dye-donating substance is Compound 11, which has the function of releasing or diffusing a diffusible dye in a pattern. This type of compound can be represented by the following general formula rLJ). (Dye - Corresponding to the mausoleum or vice versa (Dye-X)n-Y
whether it causes a difference in the diffusivity of the compound represented by
When separated, Dye is released, and represents a group having a property that causes a difference in diffusivity between the released Dye and (Dye-X), and n is 1. -! or 2, and when n is 2, the two Dye-Xs may be the same or different. Specific examples of dye-donating substances not represented by the general formula [L[] include, for example, A dye developer in which an l-' quinone type developer and a dye component are linked is disclosed in U.S. Pat. No. 3,1.34.
No. 764, No. 3,362819, No. 3, 5912
No. 00, No. 3,544,545, No. 3.4829
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-51-6
3,618, etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of the inoxazolone ring is disclosed in Japanese Patent Application Laid-Open No. 3,618/
No. 19-111,628, etc. In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is neither released nor diffused in areas where development has occurred. Unfortunately, with these methods, development and dye release and diffusion occur in parallel, making it extremely difficult to obtain images with a high S/N ratio. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form that does not have the ability to release the f' element, and is made to coexist with the reducing agent or its precursor, and after development, the reducing agent remaining without being oxidized is A system has also been devised in which a diffusible dye is released by reduction, and a specific example of a dye-donating substance used therein is disclosed in JP-A-53-11. Q
No. 827, No. 5/l-130,927, No. 56-16
4,342 and 53-35,533. On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a coupler having a diffusible dye as a leaving group and a developer are used. Substances that release diffusible dyes upon reaction with oxidants are described in British Patent No. 33 Q 524, Japanese Patent Publication No. 33165/1983, and U.S. Pat. A substance that produces a diffusible dye by reaction of a coupler having a leaving group with an oxidized form of a 3M imaging agent is described in U.S. Pat. No. 3,227,550 and others. However, in the methods that use these color developers, image contamination due to oxidative decomposition products of the color developer is a constant problem, so in order to improve this problem, we developed a method that does not require a developer.
Dye-releasing compounds that themselves have reducing properties have also been devised. Representative examples are shown below along with literature. Definitions in the general formula are described in each literature. H NH3O2-Dye U.S. Patent No.: 192a312, etc., U.S. Patent No. 4,053,312, etc. OR U.S. Patent No. 405 to 428, etc. 59-69839 JP 53-3819 JP 51-104,343 JP 51-104,343 0I (Ballast JP 51-104,343 NH302Dy e Research Disclosure Magazine 17465 H H 1 U.S. Patent No. 3.72 No. 062 H H U.S. Patent No. 3728.113 U.S. Patent No. 3,443,939 - Dye JP 58-11 et al. 537 The various dye-donating substances mentioned above are Any of them 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 Japanese Patent Application Laid-Open No. 57-84236. Among them, compounds (1) to (3), 00) to (13) described in the above page range can be used.
, (10~0, (c)~(to), (33), 0511(
) to (40) and (42 to (64)) are preferred. In addition, the following cyan and yellow dye-donating substances are also useful. 0C16H33 UC16H33 The compounds described above are examples, and are limited to these. In the present invention, the dye-donating substance is disclosed in U.S. Patent No. 2.32.
They can be incorporated into the layers of the photosensitive element by known methods such as those described in US Pat. No. 2,027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used. For example, phthanolic acid alkyl esters (e.g., butyl phthalate, dioctyl phthalate), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g., acetyl tributyl citrate), benzoic acid Ester (octyl benzoate)
, alkylamides (e.g. diethyl laurylamide),
High boiling point organic solvents such as fatty acid esters (e.g. diptoxyethyl succinate, dioctyl azelate), trimesate esters (e.g. tributyl trimesate), organic solvents with a boiling point of about 30°C to 160°C, e.g. acetic acid Lower alkyl acetates such as ethyl, butyl acetate, ethyl propionate, secondary butyl alcohol,
After being dissolved in methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in Oyagi Igyu colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Motada Special Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used. In addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. You can use it. The amount of the high boiling point organic solvent used in the present invention is 10P or less, preferably 5g per 1g of the dye-donating substance used.
It is as follows. The photosensitive material of the present invention preferably contains a reducing substance in the photosensitive element. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. It also includes a reducing agent precursor that does not have reducing properties itself, but develops reducing properties through the action of nucleophiles and heat during the development process. Examples of reducing agents used in the present invention include solid reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, human-50 xylamines, and human-9
Radins, human 9radi)・7, Bora/・Amine complexes,
hyperquinones, aminoenols, catechols, p-phenylenediamines, 3-pyrazolidinones,
h).In addition to Zroxytetronic acid, ascorbic acid, 4-amino-5-gilabrones, etc., T-H-Ja
mθS, “The theory of
the photographic process
s'' 4H4, Ea, 291-334 can also be used as the reducing agent described in -MIJI.
No. 36, No. 57-4Q245, U.S. Patent No. 4.33Q
Reducing agent precursors such as those described in No. 617 can also be used. Combinations of various developers can also be used, such as those disclosed in U.S. Pat. No. 3,039,869. / In the present invention, the amount of reducing agent added is 1 silver
0.01 to 20 mol, particularly preferably 0.01 to 20 mol
~． 1 10 moles. C. The compound of the general formula (Tl) included in the present invention is image-forming:
° I. □5k t4, 1.1. . 1. ,'ff
l□□1 Yayo. I can do that. Image formation promoters include promoters of redox reactions between oxidizing agents and reducing agents, such as silver halides and organic metal salts including organic silver salts, and dye-donating substances.
production of pigment or decomposition of pigment or mobile color, 1
It has functions such as promoting reactions such as the release of elements and promoting the movement of dyes from the photosensitive recording layer to the dye fixing layer. "1 base, nucleophilic compound, 41 yl, thermal solvent, surfactant, silver or silver ion and ÷ i al'p#Jll"b***we*-5hb.
71・These substance groups generally have multiple functions1
5. It usually has some of the promoting effects mentioned above.・ゝi, i',')ji These image formation accelerators are classified below by function and specific examples of each are shown below. However, this classification is for convenience, and in reality, one compound They often have multiple functions. (at base Examples of preferred bases include alkali metal or alkaline earth metal hydroxides secondary or tertiary bases)
Phosphate, borate, carbonate, quinolinate, metaborate; ammonium hydroxide; hydroxide of quaternary alkyl ammonium; hydroxide of other metals, etc.
Examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines):
Aromatic amines [N-alkyl substituted aromatic amines, N
-hydroxylalkyl-substituted aromatic amines and bis[p-(:)alkylamino)phenylcomethanes),
Examples include heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, especially those with pKa
is preferably 8 or more. , 1 *1""*Mlth' conversion 8'・7°
'C01'・7°'(,2
．． ',,; Tolidines, human radiates 9
-4
Acid □, Yu2゜7ao,・kind, activity, a, a. 8.i It is possible to list hardware, alcohol, and thiols.
Also, using salts or precursors of the above compounds, 'I tw-t;b. 814゜'I J (cl oil'i!'...'1 Used as a solvent when emulsifying and dispersing hydrophobic compounds.g, brss, ass.3
, wayu 6-114, -16 votes I can do it.ゝ)'□1(d) Thermal solvents, 1. Solid at ambient temperature, melts near the development temperature and acts as a solvent, including ureas, urethanes, amides, pyrudines, and sulfones. Amides, Suruke・
Hon, sulfoxides, esters, ketones 1,
Compounds such as ethers that are solid at 40° C. or lower can be used. (θ) surfactant, 1°] Pyridinium salts, ammonium salts, phosphonium salts described in JP-A-59-74547;
Examples include polyalkylene oxides described in JP-A-59-57231. (f) Compound imides that interact with silver or silver ions, air-containing heterocycles described in Japanese Patent Application No. 58-51657, thiols and thioureas described in Japanese Patent Application No. 57-222247, etc. can be mentioned. The image formation accelerator may be incorporated into either the photosensitive element or the dye fixing element, or may be incorporated into both. Further, the layers to be incorporated may be incorporated in the emulsion layer, the intermediate layer, the protective layer, the dye fixing layer, and any layer adjacent thereto. The same applies to forms in which the photosensitive layer and the dye fixing layer are provided on the same support. Image formation accelerators can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained by using several types in combination. The present invention can contain various development stoppers. The development stopper referred to here is a compound that neutralizes the base immediately after proper development, reacts with the base to lower the base concentration in the film, and stops development, or a compound that interacts with silver and silver salts. A compound that inhibits development. 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 the like. For acid precursors, for example, Japanese Patent Application No. 58-2
Examples include oxime esters described in Japanese Patent Application No. 16928 and Japanese Patent Application No. 59-48305, and compounds that release an acid by Rossen rearrangement described in Japanese Patent Application No. 59-85834, which cause a substitution reaction with a base when heated. Examples of electrophilic compounds include compounds described in Japanese Patent Application No. 59-85836. The base precursor/acid precursor ratio (molar ratio) is preferably from 1/20 to 20/1, more preferably from 115 to 5/1. Further, the light-sensitive material of the present invention may further contain a known compound that activates development and stabilizes the image at the same time. Among them, U.S. Pat.
Inthiuroniums represented by human 70-oxyethyl inthiuronium trichloroacetate, U.S. Patent No. 3
．． Bis(intiuroniums) such as L8-(3,6-thioxaoctane)bis(isothiuronium trichloroacetate) described in No. 66Q670, West German Patent Publication No. 2
Thiol compounds described in No. 162714, U.S. Pat.
．． Thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in US Pat. No. 01.2.260, bis( Preferably used are compounds having 2-carboxylic rupoxyamide as the acidic moiety, such as 2-amino-2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazoliumphenylsulfonylacetate. Additionally, azole thioether and blocked biazolithionic compounds as described in Ilgy Patent No. 76a071, and 4-7 reel- as described in U.S. Pat. No. 3,893,859.
1-Carbamyl-2-tetrazoline-5-thione compound, etc. U.S. Patent Nos. 383Q041 and 3,844
, No. 788 and No. 3.87'', 1940 are also preferably used. The present invention may contain an image toning agent if necessary. Effective toning agents include 1.24- 1 Riazole, IH-
Compounds such as tetrazole, thiouracil and L3.4-thiadiazole. Examples of preferred toning include 5-amino-1,3,4-thiadiazole-2-thiol, 3-mercapto-L2,4-) lyazole, bis(dimethylcarbamyl):) sulfite 9,6-methylthiouracil , 1-phenyl-2-tetraazoline-
Examples include 5-thione. Particularly effective toning agents are compounds capable of forming black images. The concentration of the toning agent contained varies depending on the type of heat-developable photosensitive element, processing conditions, desired image, and other factors, but generally it is about 0.0% per mole of silver in the photosensitive material. O
O1 to 01 mole. The binders used in the present invention can be contained alone or in combination. A hydrophilic material can be used as the material. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives, cellulose derivatives, starch,
Natural substances such as polysaccharides such as gum arabic and water-soluble f
Contains synthetic polymeric materials such as IJ vinyl compounds. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photosensitive materials, among other things. Is the binder of the present invention 1rr? The coating amount is less than 20gU per person, preferably 10g or less, more preferably 7g
The following are 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 cc or less of solvent per 1 g of binder, preferably 0.
A suitable amount is 5 cc or less, more preferably 0.3 cc or less. The photosensitive element of the present invention and the dye fixing element that can be included in the present invention may contain an inorganic or organic hardening agent in the photosensitive layer, other binder layers, dye fixing layer, etc. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes,
1 knee)', 71. 1, 2-7 degrees. □ Dehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (23-dihyto90oxydioxane, etc.), activated vinyl compounds (1,3,5-1-reacrylic 21 °″
'-to "9"°-°-"IJ 7):y pa°-1e
= #2"1="-2-7'o'Z / -/L
/・L2-'11 (vinylsulfonylacetamido4)ethane, etc.), haze Active halogen compound <24-:)chloro-6-hydro,,'Hroxy5
-) IJ azine, etc.), mucohalogen acids, he (mucochloric acid, mucophenoxychloroic acid, etc.),...
The m-th and a are 1. , 1 In particular, when the photosensitive element of the present invention contains a dye-donating substance represented by the general formula (LT), since the dye-donating substance is colored, irradiation prevention and halation can be prevented. Although it is not necessary to incorporate inhibitory substances or various dyes into the photosensitive element, in order to improve the sharpness of images including other photosensitive elements, Japanese Patent Publication No. 48-3692, Filter dyes, absorbent substances, etc. described in US Pat. No. 3,253,921, US Pat. No. 2,52'7,583, US Pat. These dyes are preferably thermally decolorizable, such as those described in U.S. Pat. Dyes are preferred.The photosensitive element of the present invention may optionally contain various additives known for use in heat-developable photoreceptors, for example, Research Disclosure Magazine Vol. 1.1'70. June 1978 & 17029. Examples of the additives described in this publication include plasticizers, sharpness-improving dyes, AH dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, and antifading agents. □! A system that forms images by diffusion transfer of dye □゛) 1 Hey □□□ 8 □□ Aka 8 A □ Aa 9,
:1 :1・Support same as the mode in which the photosensitive element, the dye fixing element, and 1 are coated on separate supports with 7 representative forms:': O1Kjl! R-in
, 14. ! = IJIJ, wow. The support is capable of withstanding processing temperatures. As a general support,
Glass, paper, metal and their analogues are used, but also acetyl cellulose film, cellulose film, cellulose film, vinyl acetal film, etc. ,zvxfvy;
yi, v*, yplJ car 14-17゛3
ilm, polyethylene terephthalate film 1. 1, :¥, , and the films or resin materials related to them are included. Paper supports laminated with polymers such as polyethylene may also be used.
The polyester described in □'t a725070 is preferably used. ) 9th1゛busy' The photosensitive element and the dye-fixing element are on separate supports),':! i-:1 3 There are two types of formation: one is a peeling type, and the other is a peeling-free type. In the case of the former peel-off type, the coated surface of the photosensitive element and the coated surface of the dye-fixing element are overlapped after image exposure and after heat development, and the photosensitive element is immediately peeled off from the dye-fixing layer after the transferred image is formed. . Depending on whether the final image is reflective or transmissive,
The support of the dye fixing element can be selected from an opaque support or a transparent support. Further, a white reflective layer may be coated if necessary. In the case of the latter type that does not require peeling, it is necessary that a white reflective layer be interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element.
It may be coated on any of the dye fixing elements. The support of the dye fixing element needs to be a transparent support. Hereinafter, when the dye-fixing element is on a support separate from the photosensitive dye, it may be referred to as a dye-fixing material. The photosensitive element or dye fixing element may be in the form of an electrically 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 on the chromaticity diagram using dye-donor materials exhibiting the three primary colors yellow, magenta, and cyan, the light-sensitive element of the present invention has at least three layers, each sensitive to a different wavelength region. It is necessary to have a silver halide emulsion layer with properties. At least three molecules that are photosensitive to mutually different structural regions
Typical combinations of two light-sensitive silver halide emulsion layers include a combination of a blue-sensitive emulsion layer and a red-sensitive emulsion layer, a combination of a green-sensitive emulsion layer, a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a blue-sensitive emulsion layer. Examples include no emulsion, a combination of a green-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a combination of a '-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer. Note that the infrared light-sensitive emulsion layer herein refers to a layer with a wavelength of 700 nm or more, particularly 740 nm or more.
An emulsion layer that is sensitive to light of nm or more. The photosensitive element of the present invention may have two or more emulsion layers that are sensitive to the same spectrum 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 contains a dye-donating substance that releases or forms a yellow dye, a dye-donor that releases or forms a magenta dye, and a dye-donating substance that releases or forms a magenta dye. Any one of the dye-donating substances that releases or forms cyan dye? Each must be included. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain a dye-donating substance that releases or forms dyes of different hues. If desired, two or more dye-providing substances having the same hue may be used in combination. It is advantageous to contain the dye-donor substance in a layer separate from the emulsion layer, especially when the dye-donor substance is initially colored. In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity. In addition to the above-mentioned layers, the photosensitive element of 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) is usually impregnated with an organic or inorganic matting agent for adhesion. The protective layer of the old octopus may contain a mordant, a UV absorber, etc. Each of the protective layer and the intermediate layer may be composed of two or more layers. Further, the intermediate layer may contain a reducing agent, a UV absorber, and a white pigment such as T10□ 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 has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided if necessary. Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer. The dye fixing layer may be composed of two or more layers using mordants having different mordant powers, if necessary. In addition to the above-mentioned layers, the dye fixing element can be provided with auxiliary layers such as a release layer, an 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 color migration or pigment formation or release reactions, an anti-corrosion agent to prevent color mixing of hydrophilic heat-solvent pigments, and UV absorbers. A dispersing agent, a vinyl compound for increasing dimensional stability, a fluorescent whitening agent, etc. may be impregnated. The dye fixing element may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc. depending on the purpose. These layers may be coated in the light-sensitive element using only the dye-fixing element. The configurations of the above-mentioned reflective layer, neutralization layer, and neutralization timing layer are described, for example, in U.S. Pat.
It is described in 3.364821, λ41he 644, Canadian Patent No. 92 & 559, etc. Furthermore, it is advantageous for the dye fixing element to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or it may be included in a separate layer; ] 8□Yo, 8□Work 81Y□Y6゜8,A.For the dye transfer aid, water, caustic soda, caustic potash, or an inorganic alkali metal salt is used as the dye transfer aid. In addition, low-point solvents such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, etc., or these low-boiling point solvents and aqueous solvents are used. □。。。。。。。。。。。。 If built-in, there is no need to supply transfer aid externally. □、・１ １ The above-mentioned transfer aids are incorporated into crystalline water or microcapsules;
1 or 1" - It may be incorporated as a precursor that releases the solvent at high temperatures. More preferably, a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperatures is incorporated in the photosensitive element or dye fixing element. The new aqueous thermal solvent may be incorporated into either the photosensitive element or the dye fixing element.
It may be built into both. Also, the layer to be incorporated is an emulsion layer,
Although it may be an intermediate layer, a protective layer, or a dye fixing layer, it is preferably incorporated in the dye fixing layer and/or its adjacent layer. Examples of hydrophilic heat solvents include ureas, pyridines, amides, 9 sulfonamides, imides, alcohols,
There are oximes and other heterocycles. The mordant used in the dye fixing layer can be arbitrarily selected from commonly used mordants, and among them, 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, and a polymer containing these quaternary cation groups. 4F containing one vinyl monomer unit having a tertiary amine group
The remer is described in Japanese Patent Application No. 58-169012, Japanese Patent Application No. 58-166135, etc.;・1
No. 58-226497, No. 58-23207'1, “
F11:', qffl US time 1 42823
05%・No. 4,115,124・] ″・1i13
""°°"'fi""6"15-g 1t-c"6.:
4 Preferred specific examples of dr +)mers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101 and 2,093.
,041゛1 No. 1594.961,
U.S. Patent No. 4124.386:1″・F[4,”
ゞ""3.1"'Ii4.2"3°゛. :: No. 4,45Q224, □Unexamined Japanese Patent Publication No. 48-28,225.) f, I IJ w-Qf
i'j L゛1'1lJJ: L, -C old age, U.S. Patent No. 3.70 to 690, No. 3.898,0
No. 88, same No. 3,958,995. No., special application 1982-1
No. 66135, No. 5s-r69o12.j; No. 58-232070, No. 58-2
It is described in No. 32072.j□5 and No. 59-91620, etc.;,...1 Black...1. H+, (3'1) Radiation including visible light can be used as a light source for image exposure to record an image on the heat-developable photosensitive element of the present invention.In general, a light source used for ordinary color printing can be used. , for example, in addition to tungsten lamps,
Various light sources can be used, such as a mercury lamp, a halogen lamp such as an iodine-9 lamp, a xenon lamp, a laser light source, a CRT light source, a fluorescent tube, and a light emitting diode (LED). The heating temperature in the heat development step can be developed at about 0°C to about 250°C, but particularly useful is about 10°C to about 180°C, and within this range, 140°C or higher is preferable. , particularly preferably 150'C or higher. The heating temperature in the transfer process is
Transfer is possible at a temperature ranging from the temperature in the heat development step to room temperature, but it is particularly preferable to use a temperature up to 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. A dye transfer aid (for example, water) is added between the photosensitive layer of a heat-developable photosensitive element and the dye fixing layer of a color patch fixing material to promote image transfer. It is also possible to apply a dye transfer aid to one or both of the layers before superimposing them. Examples of methods for applying the dye transfer aid to the photosensitive layer layer or the dye fixing layer include a roller coating method as described in JP-A No. 58-55907, a wire bar coating method, and a wire bar coating method as described in JP-A-58-55907. A method of applying water to a dye-fixing material using a water-absorbing member as described in Japanese Patent Application No. 55908, and a method of applying water to a dye-fixing material using a heat-developable photosensitive element and a dye-fixing element as described in Japanese Patent Application No. 58-55906. Method of applying dye transfer aid by forming beets in between, Japanese Patent Application No. 58-559
10, in which a bead is formed between a water-repellent roller and a dye fixing layer to apply a dye transfer aid; other methods include a dipping method, an extrusion method,
Various methods can be used, such as a method in which the material is applied by jetting it out from pores, a method in which the material is applied by crushing a bod, and the like. The dye transfer aid may be measured in advance and added in an amount within the range as described in Japanese Patent Application No. 58-37902, or
The amount can be adjusted by applying sufficient amount and then squeezing it with pressure using a roller or the like or drying it with heat. There is a method in which a dye transfer aid is applied, the excess dye transfer aid is squeezed out by passing between pressurized rollers, and then the dye is superimposed on the main heat-developable photosensitive abrasive.The heating means in the transfer process is heat. Heating through the entire space between the plates or in contact with the hot plate (for example, JP-A-50-62635)
No. 1), heating by rotating and contacting a heated drum or heated roller (for example, Japanese Patent Publication No. 43-10791), heating by passing through hot air (for example, Japanese Patent Publication No. 53-3273)
7), heating by passing it through an inert liquid kept at a constant temperature, heating by passing it along a heat source with a roller, belt, or guide 9 member (for example, Japanese Patent Publication No. 44-2546), etc. can. -1
However, a layer of a conductive forest material such as graphite, carbon black, or metal is applied to the pigment fixing material, and an electric current is passed through this conductive layer to heat it directly (2). The heating temperature applied in the transfer process is 60°C or higher, which is 10°C higher than the temperature in the heat developing process, although the heating temperature applied in the heat developing process is set to room temperature at a rate of -6J.
Temperatures lower than this are too low. The pressure at which the heat-developable photosensitive element and the dye-fixing element are overlapped and brought into close contact varies depending on the embodiment and the phase of the moon used.
01-1. OOklil/-0 Kashikake 1~5okg
/- is appropriate (for example, as described in Japanese Patent Application No. 58-55691). Various methods can be used to apply pressure to the heat-developable photosensitive element and the dye-fixing element, such as passing it between a pair of rollers or pressing using a plate with good smoothness. The rollers and plates used for folding and applying pressure can be heated in a range from room temperature to temperatures in the heat development process. (Example) Example 1 The following layer (r
) and (IT) were applied sequentially to prepare a photosensitive element. Application M′ of each composition in parentheses (per square meter)
showed that. Guanidine phonylacetate) (0,4,9(σ) ~ (f)
and gelatin (Ig/m'), the base precursor (0, 6, 97 m
') and gelatin (1 g/lr?) and a protective layer containing gelatin (1 g/lr?). Samples (B), (C), (D), and (E) were prepared under the same conditions.As a comparative example, a photosensitive element (F) was prepared under the same conditions as A except that it did not contain the compound of general formula (1). A method for forming a dye-fixing element having an image-receiving layer will be described below. First, gelatin hardeners H-10, 75, 9, H-20,
25,9 and 160 Wl/water, and 100 g of 10 lime-treated gelatin were mixed uniformly. This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium oxide was dispersed to form a wet film of 60 μm, and then dried. Gelatin hardener H-1゛CH2-CH802CH2(X)NHCH2CH2NH
COCH2,5O2CH=CH2 Gelatin hardener H-2 CH2L-cHsO2CH2cONHCH2・CH2C
H2NHOOCH2sO2CH=CH2 Next, polymer with the following structure (numbers represent molar ratio) 15#t-water 200i
1 and uniformly mixed with 100 g of scale 10 lime-treated gelatin. This mixed solution was uniformly applied onto the above-mentioned coating material to form a wet film of 85 μm. This sample was dried and used as a dye fixing material. The above photosensitive element (A1-(T)) was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb and then exposed on a heat block heated to 140:1 °C or 143 °C.
．． , □? ctf30□ car, car. Hey.・1 1 After immersing the dye-fixing element in water, the above-mentioned heated photosensitive elements (Al-(F)i) were stacked so that the film surfaces were in contact with each other.
1"1101 When the dye-fixing element was peeled off from the light-sensitive element, a negative magenta image was obtained on the dye-fixing element. The minimum density (Dmin) and maximum density (Dmax) of this negative image were: Macbeth reflection densitometer (RD-519)
Measure 1 using . Uh-huh. Ya□, eh. S' From the above results, this photosensitive element has a
It can be seen that I) max is stable even with variations in development time and development temperature, with a sharp dye image, and stable developability with low Dmj and n is exhibited. Example 2 Compounds of the general formula ff+ in the layer (■) (C) of Example] In place of the compound shown in Table-2, the amount relative to silver,
Furthermore, as shown in Table 2, the example compounds of the general formula 11') and /reduction (■rr) and their total amount relative to silver were tested under the same conditions as A in Example 1 (G )～(T
J) was prepared and treated in the same manner as in Examples to obtain the following results. Note that methanol solutions were used for the compounds of general formulas (■) and (III). From the above results, general formula (sha) and/or general 2G
It can be seen that by using the compound [[) in combination, changes in developability due to changes in development conditions can be further reduced. (Effects of the Invention) By using the present heat-developable color photosensitive material, development can be carried out in a short time, the resulting dye image is clear, has no fog, has a high maximum density and a low minimum density, and is variable in development conditions. Stable developability can be obtained even with respect to (3 others)

Claims (1)

[Scope of Claims] At least photosensitive silver halide and a binder on a support, which when reduced to photosensitive silver halide under high temperature conditions, generate or release a mobile dye in response to or inversely to this reaction. 1. A heat-developable color light-sensitive material having a dye-providing substance, which further contains at least one compound represented by the following general formula (I). General formula (I) R_1-S-R_2 [In the formula, R_1 and R_2 represent a substituted or unsubstituted aliphatic group, aromatic group or heterocyclic group, and R_1 and R_2
2 may form a 5- to 7-membered ring together with S. ]