EP0853255B1

EP0853255B1 - Heat developable color photosensitive material

Info

Publication number: EP0853255B1
Application number: EP98100400A
Authority: EP
Inventors: Makoto Yamada; Hideaki Naruse
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1997-01-13
Filing date: 1998-01-12
Publication date: 2001-09-05
Anticipated expiration: 2018-01-12
Also published as: DE69801530D1; EP0853255A3; DE69801530T2; EP0853255A2; ATE205306T1

Abstract

A heat developable color photosensitive material comprising a substrate carrying thereon a photosensitive silver halide, binder, a developing agent having specific structure classified into an aminophenol derivative or a phenylenediamine derivative and a compound which forms or releases a diffusive dye by reaction with an oxidized product of the developing agent, in which the material further comprises at least one of specific naphthol derivatives, phenol derivatives, pyrazolone derivatives, aminophenol derivatives, and the like. These compounds each preferably contain an organic ballasting group.

Description

The present invention relates to a color image forming method, and more particularly, to a color image forming method which can provide an excellent image in an extremely short developing time and which is not easily affected by variations in processing conditions.
Formation of an image by heat development of a silver halide photographic photosensitive material is publicly known and described, for example, in "Fundamentals of Photographic Engineering (ed. By Non-Silver Salt Photography) Corona Publishing Co., Ltd.", 1982, pp. 242 to 255 and U.S. Patent No. 4,500,626.
Heat developing photographic materials using silver halide are conventionally widely used due to their excellent photographic properties such as sensitivity, gradation and the like, as compared with the electrophotographic method, or the diazo photographic method. There are several proposals regarding methods to obtain a color image by heat development using a silver halide photosensitive material, and a coloring development method, in which a dye image is formed by the coupling reaction of an oxidized compound of a developing agent with a coupler, is listed as one method thereof. Regarding the coupler and developing agent which can be used in this coloring development method, a combination of a p-phenylene diamines reducing agent with phenol or an activated methylene coupler described in U.S. Patent No. 3,531,256, a p-amino phenol-based reducing agent described in U.S. Patent No. 3,761,270 and a combination of a sulfonamide phenol-based reducing agent with a tetravalent coupler described in U.S. Patent No. 4,021,240 are suggested.
However, this method has flaws such as the coloring of the undeveloped part of a undeveloped silver halide remaining after processing due to print out or the lapse of time, or color turbidity arising due to the existence of a color image and reduced silver on the exposed portions at the same time. To solve these flaws, a dye transferring method is proposed in which a diffusive dye is formed by heat development and transferred onto an image receiving layer.
Regarding this type of diffusion transfer type heat developing photosensitive material, there examples where a photosensitive material and an image receiving layer which can receive a dye being supported on the same substrate, and examples where an image receiving layer is supported on a substrate other than that carrying a photosensitive material.
Particularly for heat developing color photosensitive materials, it is desirable that an image receiving material in which a dye receiving layer is supported on a substrate other than that carrying photosensitive material is used, and the dye is diffused and transferred either simultaneously with or after diffusive dye formation by color development dye to obtain a dye image having high color purity.
A method is proposed in which a diffusive dye is released or formed into an image form by heat development, and transferred onto a diffusive dye fixing element. In this method, a negative dye image or a positive dye image can also be obtained by changing the kind of dye donative compound used or the kind of silver halide used. More details are described in U.S. Patent Nos. 4,500,625, 4,483,914, 4,503,137, 4,559,290, Japanese Patent Application Laid-Open (JP-A) Nos. 58-149046, 60-133449, 59-218443, 61-238056, EP No. 220,746 A2, RD 87-6199 and EP No. 210660 A2. However, there is the problem that since the color developed dye has been previously fixed on a dye donative material, greater light energy in the exposing light is required to lower the sensitivity of the photosensitive material, and a relatively large scale exposing light apparatus is used. Therefore, it is preferable to achieve a method in which a colorless coupler and a developing agent initially react and the desired pigment is diffused.
Regarding the above-described coupling method for forming an image, there are disclosed a color developing agent precursor which releases p-phenylenediamine, and a heat developing photosensitive material containing a coupler in Japanese Patent Application Publication (JP-B) No. 63-36487, JP-ANos. 5-224381 and 6-83005, a combination of a ureido aniline-based reducing agent with an active methylene-based coupler in JP-A No. 59-111,148, and a photosensitive material using a coupler which has a polymer chain in a releasable group and releases a diffusive dye in color development in JP-A No. 58-149047.
Further, JP-A No. 9-152705 discloses a photosensitive material containing novel carbamoylhydrazines. It discloses that a specified color developing agent is incorporated into a hydrophilic colloid layer formed on a substrate to form a diffusible dye from a practically colorless developing agent and coupler. JP-A No. 9-152705 represents no prior art for the present invention.
US-A-4,789,623 discloses a method for forming an image comprising heating in the presence of at least either a base and a base generating agent, a heat developer color light-sensitive material which comprises a support having thereon at least a light-sensitive silver halide, a coupler capable of coupling with an oxidation product of a developing agent, a hydrophilic binder, and at least one compound represented by Formula (Z).
However, when a color developing agent or color developing agent precursor herein described is used, higher temperature developing conditions and a longer developing time are often required to obtain an image. Particularly when an image is formed under high temperature developing conditions, control of the processing machines may be difficult and a uneven image may be formed.
Accordingly, it is the object of the present invention to provide a color image forming method which utilizes a heat developing color photosensitive material which can provide an excellent image in an extremely short developing time and is not easily affected by variations in processing conditions, to provide a color image forming method which utilizes a heat developing color photosensitive material which can lead to an image even under low temperature processing conditions, and to provide a color image forming method which utilizes a heat developing color photosensitive material with excellent storage properties.
This object has been achieved by a color image forming method, wherein a color image which is formed by a diffusive dye is diffusion-transferred onto a dye fixing material by heat developing a heat developing color photosensitive material superimposed on the dye fixing material in the presence of a small amount of water and a base, wherein said heat developing color photosensitive material comprises a substrate carrying thereon a photosensitive silver halide, a binder, a compound represented by the general formula (I) or (D) and a compound which forms or releases the diffusive dye by reaction with an oxidized product of the compound represented by the general formula (I) or (D), further comprising at least one of the compounds represented by the general formulae (II-a), (II-b), (IV-a), (IV-b), (IV-c), (IV-d), (IV-e), (IV-f) and (IV-g);
wherein, Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group, and both Q¹ and C represent an atomic group forming an unsaturated ring;
wherein, R₁ to R₄ each independently represents a hydrogen atom or substituent thereof, A represents a hydroxyl group or substituted amino group, X represents a linkage group with a valency of two or more selected from the group consisting of -NHCO -, - NHSO -, - NHSO₂ -, and -NHPO<; Y represents a bivalent linkage group, Z represents a nucleophilic group which can attack the X group when the compound represented by the formula D is oxidized, R₁ and R₂ and R₃ and R₄ each independently may bond with each other to form a ring;
wherein, Ball represents an organic ballasting group which allows the compounds represented by the formulae co become non-diffusive, when R¹ is non-diffusive, Ball may not be required;
Y¹ represents a carbon atom group required for completing a benzene nucleus or naphthalene nucleus;
R¹ represents an alkyl group. cycloalkyl group, aralkyl group, aryl group, amino group or heretocyclic group;
R² represents a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group. carbamoyl group, sulfamoyl group. alkylsulfonyl group, arylsulfonyl group, acylamino group. alkylthio group, or arylthio group;
n represents an integer from 0 to 5, and when n is 2 to 5, R¹ may be the same or different, or a plurality may bond together to form a ring;
when Y¹ represents an atomic group required for completing a caphthalene nucleus, Ball and R² can be bonded to any one of the rings formed;

HO-R²⁹

¹¹

²

R₂₃ represents an alkyl group, an aryl group or a heterocyclic group;
Y² represents an aryl group, an alkyl group, a heterocyclic group, a -P(=O) (Rb) -Ra group, or a -C(=O)-Ra group; R^'24 represents an alkylene group, an arylene group or an aralkylene group; R²⁴ represents an alkyl group or an aryl group; wherein, Y² and R²⁴ can not represent an aLkyl group simultaneously; Ra and Rb each independently represent an alkyl group, an aryl group, an amino group, an alkoxy group, or an aryloxy group;
n represents an integer from 1 to 5;
R²⁵ represents a hydrogen atom, an alkyl group, an aryl group, a phenylsulfonyl group, or an acyl group; R²⁶ and R²⁴ have the same meaning; R²⁵ and R²⁶ may close a ring co form a 5. to 7-membered ring;
R²⁷ and R²⁸ have the same meaning as R²⁴, and may close ring co form a 5- co 7-membered ring; and R²⁹ represents an alkyl group having 12 to 50 carbon atoms in total;
represents a 5 to 7-membered heterocyclic ring;
with the proviso that the compound
is excluded as a compound of formula (D).

The present invention will be described below in detail.
First, compounds represented by the general formula (I) used in the present invention will be described in detail.
In the general formula (I), Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group. Among them, a carbamoyl group is preferred, and a carbamoyl group having a hydrogen atom on a nitrogen atom is particularly preferable.
As the carbamoyl group, a carbamoyl group having 1 to 50 carbon atoms is preferable and one having 6 to 40 carbon atoms is more preferable. Specific examples thereof include a carbamoyl group, a methylcarbamoyl group, an ethylcarbamoyl group, an n-propylcarbamoyl group, a sec-butylcarbamoyl group, an n-octylcarbamoyl group, a cyclohexylcarbamoyl group, a tert-butylcarbmoyl group, a dodecylcarbamoyl group, a 3-dodecyloxypropylcarbamoyl group, an octadecylcarbamoyl group, a 3-(2,4-tert-pentylphenoxy)propylcarbamoyl group, a 2-hexyldecylcarbamoyl group, a phenylcarbamoyl group, a 4-dodecyloxyphenylcarbamoyl group, a 2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group, a naphthylcarbamoyl group, a 3-pyridylcarbamoyl group, a 3,5-bis-octyloxycarbonylphenylcarbamoyl group, a 3,5-bis-tetradecyloxyphenylcarbamoyl group, a benzyloxycarbamoyl group and a 2,5-dioxo-1-pyrrolidinylcarbamoyl group.
As the acyl group, an acyl group having 1 to 50 carbon atoms is preferable, and one having 6 to 40 carbon atoms is more preferable. Specific examples thereof include a formyl group, an acetyl group, a 2-methylpropanoyl group, a cyclohexylcarbonyl group, an n-octanoyl group, a 2-hexyldecanoyl group, a dodecanoyl group, a chloroacetyl group, a trifluoroacetyl group, a benzoyl group, a 4-dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group and a 3-(N-hydroxyl-N-methylaminocarbonyl)propanyl group.
As the alkoxycarbonyl group and aryloxycarbonyl group, an alkoxycarbonyl group having 2 to 50 carbon atoms and an aryloxycarbonyl group having 6 to 50 carbon atoms are preferable and an alkoxycarbonyl group and aryloxycarbonyl group each having 6 to 40 carbon atoms are more preferable. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an isobutyloxycarbonyl group, a cyclohexyloxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group, a 4-octyloxyphenoxycarbonyl group, a 2-hydroxymethylphenoxycarbonyl group and a 4-dodecyloxyphenoxycarbonyl group.
As the sulfonyl group, a sulfonyl group having 1 to 50 carbon atoms is preferable, and one having 6 to 40 carbon atoms is more preferable. Specific examples thereof include a methylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a 2-hexyldecysulfonyl group, a 3-dodecyloxypropylsulfonyl group, a 2-n-octyloxy-5-t-octylphenylsulfonyl group and a 4-dodecyoxyphenylsulfonyl group.
As the sulfamoyl group, a sulfamoyl group having 0 to 50 carbon atoms is preferable, and one having 6 to 40 carbon atoms is more preferable. Specific examples thereof include a sulfamoyl group, an ethylsulfamoyl group, a 2-ethylhexylsulfamoyl group, a decylsulfamoyl group, a hexadecylsulfamoyl group, a 3-(2-ethylhexyloxy)propylsulfamoyl group, (2-chloro-5-dodecyloxycarbonylphenyl) sulfamoyl group and 2-tetradecyloxyphenylsulfamoyl group.
Both Q¹ and C represent an atom group which forms an unsaturated ring, and as the unsaturated ring formed, a 3 to 8-membered ring is preferable, and 5 to 6-membered ring is more preferable. Examples thereof include a benzene ring, a pyridine ring, a pyradine ring, a pyrimidine ring, a pyridazine ring, a 1,2,4-triazine ring, a 1,3,5-triazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a 1, 2 , 3 - triazole ring, a 1,2,4-triazole ring, a tetrazole ring, a 1,3,4-thiadiazole ring, a 1,2,4-thiadiazole ring, a 1,2,5-thiadiazole ring, a 1,3,4-oxadiazole ring, a 1,2,4-oxadiazole ring, a 1,2,5-oxadiazolering, a thiazole ring, an oxazole ring, an isothiazole ring, an isooxazole ring and a thiophene ring. And condensed rings obtained by condensation of these rings are also preferably used.
The rings may further have a substituent, and examples of the substituent include a straight or branched, linear or cyclic alkyl group having 1 to 50 carbon atoms (such as trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl and dodecyl), a straight or branched, linear or cyclic alkenyl group having 2 to 50 carbon atoms (such as vinyl, 1-methylvinyl and cyclohexene-1-yl), an alkynyl group having 2 to 50 carbon atoms in total (such as ethynyl and 1-propynyl), an aryl group having 6 to 50 carbon atoms (such as phenyl, naphthyl and anthryl), an acyloxy group having 1 to 50 carbon atoms (such as acetoxy, tetradecanoyloxy and benzoyloxy), an alkoxycarbonyloxy group having 2 to 50 carbon atoms (such as methoxycarbonyloxy and 2-methoxyethoxycarbonyloxy groups), an aryloxycarbonyloxy group having 7 to 50 carbon atoms (such as a phenoxycarbonyloxy group), a carbamoyloxy group having 1 to 50 carbon atoms (such as N,N-dimethylcarbamoyloxy), a carbonamide group having 1 to 50 carbon atoms (such as formamide, N-methylacetoamide, acetoamide, N-methylformamide and benzamide), a sulfonamide group having 1 to 50 carbon atoms (such as methanesulfonamide, dodecanesulfonamide, benzenesulfonamide and p-toluenesulfonamide), a carbamoyl group having 1 to 50 carbon atoms (such as N-methylcarbamoyl, N,N-diethylcarbamoyl and N-mesylcarbamoyl), a sulfamoyl group having 0 to 50 carbon atoms (such as N-butylsulfamoyl, N,N-diethylsulfamoyl and N-methyl-N-(4-methoxyphenyl)sulfamoyl), an alkoxy group having 1 to 50 carbon atoms (such as methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, dodecyloxy and 2-(2,4-di-t-pentylphenoxy)ethoxy), an aryloxy group having 6 to 50 carbon atoms (such as phenoxy, 4-methoxyphenoxy and naphthoxy), an aryloxycarbonyl group having 7 to 50 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl), an alkoxycarbonyl group having 2 to 50 carbon atoms (such as methoxycarbonyl and t-butoxycarbonyl), an N-acylsulfamoyl group having 1 to 50 carbon atoms (such as N-tetradecanoylsulfamoyl and N-benzoylsulfamoyl), an N-sulfamoylcarbamoyl group having 1 to 50 carbon atoms (such as N-methanesulfonylcarbamoyl group), an alkylsulfonyl group having 1 to 50 carbon atoms (such as methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl and 2-hexyldecylsulfonyl), an arylsulfonyl group having 6 to 50 carbon atoms (such as benzensulfonyl, p-toluenesulfonyl and 4-phenylsulfonylphenylsulfonyl), an alkoxycarbonylamino group having 2 to 50 carbon atoms (such as ethoxycarbonylamino), an aryloxycarbonylamino group having 7 to 50 carbon atoms (such as phenoxycarbonylamino and naphthoxycarbonylamino), an amino group having 0 to 50 carbon atoms (such as amino, methylamino, diethylamino, diisopropylamino, anilino and morpholino), an ammonio group having 3 to 50 carbon atoms (such as trimethylammonio and dimethylbenzylammonio groups), a cyano group, a nitro group, a carboxyl group, a hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 50 carbon atoms (such as methanesulfinyl and octanesulfinyl), an arylsulfinyl group having 6 to 50 carbon atoms (such as benzenesulfinyl, 4-chlorophenylsulfinyl and p-toluenesulfinyl), an alkylthio group having 1 to 50 carbon atoms (such as methylthio, octylthio and cyclohexylthio), an arylthio group having 6 to 50 carbon atoms (such as phenylthio, naphthylthio), a ureido group having 1 to 50 carbon atoms (such as 3-methylureido, 3,3-dimethylureido and 1,3-diphenylureido), a heterocyclic group having 2 to 50 carbon atoms (such as 3 to 12-membered monocyclic or condensed rings containing at least one hetero atom such as nitrogen, oxygen and sulfur, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazoyl, morpholino, 2-quinolyl, 2-benzoimidazolyl, 2-benzothiazolyl and 2-benzooxazolyl), an acyl group having 1 to 50 carbon atoms (such as acetyl, benzoyl and trifluoroacetyl), a sulfamoylamino group having 0 to 50 carbon atoms (such as N-butylsulfamoylamino and N-phenylsulfamoylamino), a silyl group having 3 to 50 carbon atoms (such as trimethylsilyl, dimethyl-t-butylsilyl and triphenylsilyl), and a halogen atom (such as a fluorine, chlorine or bromine atoms). . The above-described substituents may further have a substituent, and examples thereof include those listed above.
The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less and further preferably 30 or less. To import sufficient diffusion abilities to the dye which is produced by the reaction of a color developing agent with a coupler in the present invention, -the total number of carbon atoms of an unsaturated ring formed from Q and C and a substituent thereof is preferably from 1 to 30, and more preferably from 1 to 24, and most preferably from 1 to 18.
When the ring formed from Q and C is composed solely of carbon atoms (such as benzene, naphthalene and anthracene rings), the total σ value of Hammett substituent constants (in the case of 1,2, 1,4, --- position relative to C, σp value is adopted, and in the case of 1,3, 1,5, --- position relative to C, σm value is adopted) of all substituents is preferably 0.8 or more, more preferably 1.2 or more and most preferably 1.5 or more.
The details of Hammett substituent constants σp and σm are described in, for example, N. Inamoto, "Hammett rule - structure and reactivity ·" (Maruzen), "New Experimental Chemical Seminar 14 Synthesis and Reaction of Organic Compounds V" p. 2605 (Japan Chemical Institute edit., Maruzen), T. Nakaya, "Theoretical Organic Chemistry Commentary p.217 (Tokyo Chemical Coterie) and Chemical Review, vol. 91, pp. 165 to 195 (1991).
Specific examples of the color developing agent represented by the general formula (I) will be described below, however, the present invention is not limited in range thereto.
Next, general synthesis methods for the compound of the present invention are described below. A typical synthesis method for a typical compound used in the present invention is described below. The other compounds can be synthesized in the same manner as described below.

Synthesis Example 1. Synthesis of exemplary compound (1)

The compound (1) was synthesized according to the following synthesis route.

Synthesis of compound (A-2)

53.1 g of 1,2-dichloro-4,5-dicyanobenzene (A-1) (CAS Registry No. 139152-08-2) was dissolved in 1.1 liters of N,N-dimethylformamide (DMF), to this was added dropwise 268 g of an aqueous methylmercaptane sodium salt solution (15%) at room temperature over a period of 1 hour, and the resulting mixture was stirred for 1 hour at 60°C. The reaction solution was cooled to room temperature, water was added to this solution, and the resulting mixture was stirred for 30 minutes. The white solid produced was collected by filtration, and washed with water, and dried. Yield: 46.5 g, 78.1%

Synthesis of compound (A-3)

41.1 g of compound (A-2) was suspended in 400 ml of acetic acid, and to this was added dropwise a solution obtained by dissolving 89.3 g of potassium permanganate into 400 ml of water over a period of 1 hour while water cooling. The mixture was allowed to stand overnight at room temperature, then, 2 liters of water and 2 liters of ethyl acetate were added, and the resulted mixture was subjected to Celite filtration. The filtrate was separated, and the resulting organic layer was washed with water, an aqueous sodium hydrosulfite solution, a sodium hydrogencarbonate solution and a sodium chloride solution before drying over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, to the residue was added a mixed solvent composed of ethyl acetate and hexane for crystallization to give 29.4 g of compound (A-3) as a white solid. Yield 55.0%

Synthesis of compound (A-4)

29.4 g of compound (A-3) was dissolved in 200 ml of dimethylsulfoxide (DMSO), to this was added dropwise 8.7 g of hydrazine monohydrate over a period of 15 minutes while water-cooling, and the mixture was further stirred for 10 minutes while water-cooling. The reaction solution was poured into water, and the produced yellow solid was collected by filtration, washed with water, and dried. Yield: 17.4 g, 70.9%

Synthesis of exemplary compound (1)

11.8 g of compound (A-4) was dissolved in 50 ml of tetrahydrofuran, to this was added dropwise 4.7 g of propyl isocyanate over a period of 30 minutes at room temperature, and the mixture was further stirred for 1 hour. The reaction mixture was poured into water, and extracted with ethyl acetate. The organic layer was washed with a hydrochloric acid solution and a sodium chloride solution, before drying over anhydrous magnesium sulfate, and after filtration the solvent was removed. The residue was crystallized out from a mixed solvent of ethyl acetate-hexane (1:10) to give 14.5 g of exemplary compound (1) as a white solid. Yield: 90.2%

Synthesis Example 2. Synthesis of exemplary compound (5)

Exemplary compound (5) was synthesized according to the following synthesis route.

Synthesis of compound (A-6)

44.5 g of compound (A-5) (CAS Registry No. 51461-11-1) was dissolved in 500 ml of ethyl acetate, and to the resulting mixture was added 500 ml of water to which 25 g of sodium hydrogencarbonate had been dissolved. To this solution was added dropwise 16.4 g of phenyl chlorocarbonate over a period of 30 minutes at room temperature, and the resulting mixture was stirred for further 1 hour. The reaction mixture was separated, and the organic layer was washed with a sodium chloride solution before drying over anhydrous magnesium sulfate, and after filtration, the solvent was distilled off to give 54.0 g of compound (A-6) as a pale yellow oil. Yield: 95.6%

Synthesis of exemplary compound (5)

5.0 g of compound (A-4), 13.0 g of compound (A-9) and 0.50 g of DMAP (N,N-dimethylaminopyridine) were dissolved in 100 ml of acetonitrile, and the mixture was stirred for 3 hours at 60°C. The reaction mixture was poured into water, and extracted with ethyl acetate. The resulted organic layer was washed with a sodium hydrogencarbonate solution, a hydrochloric acid solution, and a sodium chloride solution before drying over anhydrous magnesium sulfate. After filtration, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluant: ethyl acetate/hexane = 1/2), and crystallized out from hexane to give 7.5 g of exemplary compound (5) as a white solid.

Synthesis Example 3. Synthesis of exemplary compound (15)

Exemplary compound (15) was synthesized according to the following synthesis route.

Synthesis of exemplary compound (15)

4.6 g of triphosgene was dissolved in 100 ml of THF, to which was added dropwise 13.6 g of compound (A-7) (CAS Registry No. 61053-26-7) over a period of time of 10 minutes at room temperature, and to this was further added dropwise 18.7 ml of triethylamine over a period of 10 minutes at room temperature. The mixture was reacted for 30 minutes to obtain a solution of compound (A-8). To this reaction solution was added 9.0 g of compound (A-9) in several portions over a period of time of 10 minutes at room temperature. The mixture was further stirred for 1 hour, then poured into water, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with a sodium hydrogencarbonate solution, a hydrochloric acid solution, and a sodium chloride solution before drying over anhydrous magnesium sulfate, and after filtration, the solvent was distilled off. The residue was purified by silica gel column chromatography, and crystallized out from an ethyl acetate/hexane = 1/10 mixed solution to give exemplary compound (15) as a white solid.
Next, the compound used in the present invention represented by the general formula (D) will be described below.
The compound represented by the general formula (D) represents a developing agent: classified under aminophenol derivatives and phenylenediamine derivatives. In the formula, R₁ to R₄ each independently represent a hydrogen atom or substituent thereof, and examples thereof include a halogen atom (such as chloro and bromo groups), an alkyl group (such as methyl, ethyl, isopropyl, n-butyl and t-butyl groups), an aryl group (such as phenyl group, tolyl group and xylyl groups), a carbon amide group (such as acetylamino, propionylamino, butyloylamino and benzoyl amino groups), a sulfonamide group (such as methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino and toluenesulfonylamino groups), an alkoxy group (such as methoxy and ethoxy groups), an aryloxy group (such as a phenoxy group), an alkylthio group (such as methylthio, ethylthio and butylthio groups), an arylthio group (such as phenylthio and tolylthio groups), a carbamoyl group (such as methylcarbamoyl, dimethylcarbaomyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, dipiperidinocarbamoyl, morpholinocarbamoyl, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl and benzylphenylcarbamoyl groups), a sulfamoyl group (such as methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidinosulfamoyl, morpholinosulfamoyl, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfanoyl, benzylphenylsulfamoyl groups), a cyano group, a sulfonyl group (such as methanesulfonyl, ethanesulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl and p-toluenesulfonyl groups), an alkoxycarbonyl group (such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl groups), an aryloxycarbonyl group (such as a phenoxycarbonyl group), an acyl group (such as acetyl, propionyl, butyloyl, benzoyl and alkylbenzoyl groups), a ureido group (such as methylaminocarbonamide and diethylaminocarbonamide groups), a urethane group (such as methoxycarbonamide and butoxycarbonamide groups) and an acylthio group (such as acetyloxy, propionyloxy and butyloyloxy groups). Among R₁ to R₄, R₂ and/or R₄ is preferably a hydrogen atom. When A is a hydroxyl group, the total value of Hammett constants σp of R₁ to R₄ is preferably 0 or more, and when A is a substituted amino group, the total value of Hammett constants σp of R₁ to R₄ is preferably 0 or less.
A represents a hydroxyl group or substituted amino group (such as dimethylamino, diethylamino and ethylhydroxyethylamino groups), and preferably a hydroxyl group. X represents a linkage group having a valency of two or more selected from -NHCO-, -NHSO-, -NHSO₂- and -NHPO<, and among them, -NHCO-, -NHSO₂- and -NHPO< are preferable. Z represents a nucleophilic group which can effect a nucleophilic attack on a carbon atom, sulfur atom or phosphorus atom of X to form a dye, after the coupling reaction of a coupler with an oxidized compound produced by the reduction of a silver halide by the present compound. In this nucleophilic group, moieties manifesting nucleophilicity asis generally the case in organic chemistry, include an atom having a non-covalent electron pair (such as nitrogen, phosphorus, oxygen, sulfur and selenium atoms) and anionic species (such as nitrogen, oxygen, carbon and sulfur anions). Examples of this nucleophilic group are groups having partial structures and decomposed materials thereof as listed in the following specific examples. In the following specific examples, an atom underlined thus "=" has nucleophilicity. Examples of this nucleophilic group are groups having partial structures and decomposed materials thereof as listed in the following specific examples. In the following specific examples, an atom underlined thus "=" has nucleophilicity.
Y represents a bivalent linkage group. This linkage group represents a group in which Z is linkage in such a position as to enables an intramolecular nucleophilic attack onto X via Y. In practice, it is preferable that the atoms in the transition condition when the nucleophilic group effects a nucleophilic attack onto X are connected so as to form a 5 or 6-membered ring.
Preferable examples of such a linkage group Y include a 1,2- or 1,3-alkylene group, a 1,2-cycloalkylene group, a Z-vinylene group, a 1,2-arylene group, a 1,8-naphthylene group, and the like. n represents an integer of 1 or more. R₁ and R₂ and, R₃ and R₄ may each independently bond with each other to form a ring.
As a method for adding the developing agent represented by the general formula (D), it is possible that a coupler, developing agent, and solvent having a high boiling point (such as alkyl phosphate, alkyl phthalate) are first mixed and dissolved in a solvent having a low boiling point (such as, ethyl acetate and methyl ethyl ketone), and the resulting solution dispersed in water using an emulsifying dispersion method known in the art before the addition of the developing agent. Further, the developing agent can also be added by a solid dispersion method described in Japanese Patent Application Laid-Open (JP-A) No. 63-271339.
It is preferable that the compound represented by the general formula (D) is an oil-soluble compound when the compound is added by the emulsifying dispersion method from among the above-described methods. For this purpose, it is required that at least one group having ballast properties is included. The ballast group herein represents an oil soluble group containing an oil-soluble partial structure having 8 to 80 and preferably 10 to 40 carbon atoms. For this structure, it is required that a ballast group having 8 or more carbon atoms is contained in any of R₁ to R₄, X, Y or Z. Preferably, the ballast group is contained in either Y or Z, with the number of carbon atoms being preferably from 8 to 80, and more preferably from 8 to 20.
The developing agent used in the present invention can be synthesized by combining organic synthesis reactions in stepwise fashion. Typical compound synthesis examples are described below.

A developing agent D-1 was synthesized by the synthesis route shown below (Scheme-1).

(1) Synthesis of compound A

Into a 2 L three-necked flask equipped with a condenser and thermometer were charged 600 ml of acetonitrile and 178 g (1 mol) of 2,6-dichloro-4-aminophenol, and the mixture was kept at 0°C or lower by stirring it over a methanol-ice bath. When 81 ml (1 mol) of pyridine was added to this mixture while ventilcting it with nitrogen, an exothermic reaction occurred and a homogeneous solution was obtained. The temperature was lowered to 5°C or less, and a solution, obtained by dissolving 184 g of o-sulfobenzoic anhydride (1 mol) in 250 ml of N,N-dimethylacetoamide (DMAc), was carefully added so that the temperature in the flask did not exceed 35°C. After completion of the addition, the mixture was further stirred for 1 hour at room temperature to complete the reaction, then, 200 g (1.3 mol) of phosphorus oxychloride was added to this dropwise. An exothermic reaction occurred as a result of the addition, and the temperature increased to about 60°C. The temperature was kept at 60 to 70°C by using a hot water bath, and the reaction was continued for 5 hours while stirring. After completion of the reaction, this reaction mixture was added to 10 L of ice water, and the deposited crystals were separated by filtration. The resultant crude crystals were re-crystallized from a mixed solvent of acetonitrile-DMAc: to obtain 300 g of crystals of compound A (yield: 87%).

(2) Synthesis of developing agent D-1

Into a 1 L three-necked flask equipped with a condenser and thermometer were charged 172 g (0.5 mol) of compound A, 600 ml of DMAc, 140 ml (1 mol) of triethylamine, and 122 g (0.5 mol) of lauryloxypropylamine, and they were reacted for 3 hours at a temperature of 70°C while stirring. After completion of the reaction, this reaction mixture was added to 10 L of ice-hydrochloric acid solution, and the deposited crystals were separated by filtration. The resultant crude crystals were re-crystallized from ethanol to obtain 265 g of crystals of a developing agent D-1 (yield: 90%).

A developing agent D-7 was synthesized-by a synthesis route as shown below (Scheme-2).

(1) Compound B→C

Into a 1 L eggplant-type flask were charged a rotator for a magnetic stirrer, 228 g (1 mol) of compound B, and 155 g (1.2 mol) of di-n-butylamine, a gas inlet tube was attached to this flask, and the tube was connected to an aspirator through a pressure resistant rubber tube. The solution was stirred using a magnetic stirrer while reduced pressure was maintained by water flow, and the temperature thereof was raised up to 120°C to cause deposition of crystals of phenol in the glass section of the aspirator. The reaction was continued for 4 hours, and when the deposition of phenol crystals stopped, the temperature was lowered again to room temperature. This reaction mixture was added to 3 L of a hydrochloric acid solution, and the deposited crystals were separated by filtration. This crude crystal was re-crystallized from 1 L of methanol to obtain 242 g of crystals of compound C (yield 92%).

(2) Compound C→D

Into a 5 L beaker was charged 66 g (0.25 mol) of compound C, then 100 ml of methanol, 250 g (1.8 mol) of potassium carbonate, and 500 ml of water were added and they were dissolved completely. This solution was kept at 0°C or lower while stirring. Meanwhile, another solution was prepared by dissolving 65 g (0.375 mol) of sulfanilic acid and 16.5 g of sodium hydroxide into 130 ml of water. To this was added 90 ml of concentrated hydrochloric acid to prepare a slurry solution. The prepared solution was vigorously stirred while being maintained at 0°C or lower, and to this was gradually added a solution prepared by dissolving 27.5 g (0.4 mol) of sodium nitrite into 50 ml of water, to produce a diazonium salt. This reaction was effected with ice added appropriately to maintain the temperature at 0°C or lower. The diazonium salt thus obtained was gradually added to the solution of the compound B which had been continually stirred. This reaction was also effected by appropriately adding ice to maintain the temperature at 0°C or lower. As the addition proceeded, the solution turned red due to the azo dye. After completion of the addition, the solution was further reacted for 30 minutes at 0°C or lower, and when dissipation of the raw materials was confirmed, 500 g (3 mol) of sodium hydrosulfite in the form of a powder was added. When this solution was heated to 50°C, reduction of the azo group occurred with intense foaming. When the foaming stopped and the solution had decolorized to a yellowish clear solution, it was cooled to 10°C and deposits of crystals were found. The deposited crystals were separated by filtration, and the resultant crude crystals were re-crystallized from 300 ml of methanol to obtain 56 g of crystals of compound D (yield: 80%).

(3) Compound D→E

Into a 1 L three-necked flask equipped with a condenser were charged 200 ml of acetonitrile, 56 g (0.2 mol) of compound D, and 16 ml (0.2 mol) of pyridine, and to this was added 44 g (0.2 mol) of o-nitrobenzenesulfonyl chloride over a period of 30 minutes. After completion of the addition, the mixture was further stirred at room temperature for 2 hours to complete the reaction. This reaction mixture was added to 3 L of a hydrochloric acid solution, and the deposited crystals were separated by filtration. The crude crystals were re-crystallized from methanol to obtain 86 g of crystals of compound E (yield: 93%).

(4) Compound E→F

Into a 3 L three-necked flask equipped with a condenser were charged 1 L of isopropanol, 100 ml of water, 10 g of ammonium chloride, and 100 g of a reduced iron powder, and the mixture was heated while stirring over a water vapor bath until the isopropanol was gently reduced. Under reflux conditions, stirring was continued for about 15 minutes. To this was gradually added 100 g of compound E over a period of 30 minutes. Intense reduction occurred with each addition, as the reduction reaction progressed. After completion of the addition, the solution was further reacted for 1 hour under reflux. This reaction mixture was filtered through a Buchner funnel on which celite was spread in a heated condition. The residue was further washed with methanol, and then was also filtered and added to the filtrate. When the filtrate was condensed under reduced pressure to about 300 cc, crystals were deposited, then this filtrate was cooled to grow the crystals. The crystals were filtered, and washed with methanol before drying to obtain 80 g of crystals of compound F (yield: 85%).

(5) Compound F→Developing agent D-7

Into a 1 L three-necked flask equipped with a condenser and a thermometer were charged 300 ml of tetrahydrofuran and 87 g (0.2 mol) of compound F. The mixture was stirred at room temperature. To this was added dropwise 59.1 g (0.2 mol) of octadecyl isocyanate. In this procedure, the temperature was maintained at 30°C or less. After the addition, the mixture was stirred for 2 hours, then the reaction mixture was added to 5 L of ice water. When crystals were deposited, they were separated by filtration, and re-crystallized from 600 ml of isopropanol to obtain 139 g of crystals of a developing agent D-7 (yield: 95%).
Specific examples of the color developing agent represented by general formula D may include, but are not limited to, the following developing agents.
The color developing agent used in the present invention represented by the general formula (I) or (D) is used together with a compound (coupler) which forms a dye by an oxidation coupling reaction. In the present invention, what is called a "two equivalent coupler" in which the coupling position is substituted, and which is used in general silver salt photography using a p-phenylenediamine developing agent as a developing chemical is preferable. Details of the above-described coupler are described, for example, in T. H. James, The Theory of the Photographic Process, 4th. Ed., Macmillan, 1977, pp. 291-334, pp. 354-361, and in Japanese Patent Application Laid-Open (JP-A) Nos. 58-12353, 58-149046, 58-149047, 59-11114, 59-124399, 59-174835, 59-231539, 59-231540, 60-2951, 60-14242, 60-23474 and 60-66249.
Examples of the coupler preferably used in the present invention will be described below.
Examples of the coupler preferably used in the present invention may include compounds having structures described in the following general formulae (1) to (12). These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol, naphthol or pyrrolotriazole respectively, and are well known in the art.
The compounds represented by the general formulae (1) to (4) are couplers called active methylene type couplers which are described in U.S. Patent Nos. 3,933,501, 4,022,620, 4,248,961, Japanese Patent Application Publication (JP-B) No. 58-10739, BP Nos. 1,425,020, 1,476,760, U.S. Patent Nos. 3,973, 968, 4,314,023, 4,511,649 and EP No. 249,473A. In these general formulae, R³⁴ represents an acyl group, a cyano group, a nitro group, an aryl group, a hetero cyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl group each of which may have a substituent.
In the compounds represented by the general formulae (1) to (3), R³⁵ represents an alkyl group, an aryl group or a hetero cyclic group which may have a substituent. In the general formula (4), R³⁶ represents an aryl group or a hetero cyclic group which may have a substituent. Examples of the substituents that R³⁴, R³⁵ and R³⁶ may have include the examples of the substituents on a ring formed from Q¹ and C.
In the compounds represented by the general formulae (1) to (4), R³⁴ and R³⁵ may be linked to each other to form a ring and R³⁴ and R³⁶ may be linked to each other to form a ring.
The compound represented by the general formula (5) is a coupler referred to as a 5-pyrazolone-based coupler. In the general formula (5), R³⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R³⁸ represents a phenyl group or a phenyl group having one or more substituents selected from a halogen atom, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, and an acylamino group.
In the 5-pyrazolone-based coupler represented by the general formula (5), R³⁷ is preferably an aryl group or acyl group, and R³⁸ is preferably a phenyl group having one or more substituents selected from halogen atoms.
More specifically, R³⁷ may include aryl or acetyl groups such as a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecaneamidephenyl group, a 2-chloro-5-(3-octadecenyl-1-succinimide)phenyl group, a 2-chloro-5-octadecylsulfoneamidephenyl group and a 2-chloro-5-[2-(4-hydroxy-3-t-butylphenoxy)tetradecaneamide]phenyl, acyl groups such as a 2-(2,4-di-t-pentylphenoxy)butanoyl group, benzoyl group and a 3-(2,4-di-t-amylphenoxyacetoamide)benzoyl group, and these groups may further have a substituent, which is an organic substituent or halogen atom which is connected via a carbon atom, oxygen atom, nitrogen atom or sulfur atom. Y³ is as defined above.
R³⁸ preferably may include a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chloropheyl group.
The compound represented by the general formula (6) may be a coupler referred to as a pyrazoloazole-based coupler. In the general formula (6), R³⁹ represents a hydrogen atom or a substituent. Q³ represents a non-metal atom group required for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).
Among the pyrazoloazole based couplers represented by the general formula (6), imidazo[1,2-b]pyrazoles described in U.S. patent No. 4,500,630, pyrazolo[1,5-b]-1,2,4-triazoles described in U.S. patent No. 4,500,654 and pyrazolo[5,1-c]-1,2,4-triazoles described in U.S. patent No. 3,725,067 are preferable from the point of the spectral absorption properties of the color developing dye.
The details of substituents on an azole ring represented by R₃₉, Q³ are described, for example, in U.S. patent No. 4,540,654, 2nd column, lines 41 to 8th column, line 27. Preferable examples thereof may include a pyrazoloazole coupler in which a branched alkyl group directly bonds to the 2, 3 or 6-position of a pyrazolotriazole group described in Japanese Patent Application Laid-Open (JP-A) No. 61-65,245, a pyrazoloazole coupler containing a sulfoneamide group in the molecule described in Japanese Patent Application Laid-Open (JP-A) No. 61-65245, U.S. Patent No. 5, 541, 501, a pyrazoloazole coupler having an alkoxyphenylsulfoneamide ballast group described in Japanese Patent Application Laid-Open (JP-A) No. 61-147254, a pyrazoloazole coupler having an alkoxy group and aryloxy group in the 6-position described in Japanese Patent Application Laid-Open (JP-A) No. 62-209457 or 63-307453, and a pyrazoloazole coupler having a carbonamide group in the molecule described in Japanese Patent Application No. 1-22279.
The compounds represented by the general formulae (7) and (8) are couplers referred to as a phenol-based coupler and naphthol-based coupler, respectively. In these general formulae, R⁴⁰ represents a hydrogen atom or a group selected from -CONR⁴²R⁴³, -SO₂NR⁴²R⁴³, -NHCOR⁴², -NHCONR⁴²R⁴³ and -NHSO₂NR⁴²R⁴³. R⁴² and R⁴³ represent a hydrogen atom or a substituent thereof. In the general formulae (7) and (8), R⁴¹ represents a substituent, l represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R⁴¹ may be different for each of them. The substituents of R⁴² to R⁴³ have the same definitions as defined in the substituents on a ring formed from Q¹ and C.
Preferable examples of the phenol-based coupler represented by the formula (7) may include 2-alkylamino-5-alkylphenol-based couplers described in U.S. patent Nos. 2,369,929, 2,801,171, 2,772,162, 2,895,826 and 3,772,002, 2,5-dialkylaminophenol-based couplers described in U.S. patent Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, OLS 3,329,729 and Japanese Patent Application Laid-Open (JP-A) No. 59-166956, 2-phenylureido-5-acylaminophenol-based couplers described in U.S. patent Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767.
Preferable examples of the naphthol coupler represented by the formula (8) may include 2-carbamoyl-1-naphthol-based couplers described in U.S. patent Nos. 2,474,293, 4,052,212, 4,146,396, 4,282,233 and 4,296,200, as well as 2-carbamoyl-5-amide-1-naphthol-based couplers described in U.S. patent No. 4,690,889.
The compounds represented by the general formulae (9) to (12) are couplers each referred to as pyrrolotriazole. In these general formulae, R⁵², R⁵³ and R⁵⁴ represent a hydrogen atom or a substituent thereof. Y³ is as defined above. The substituents of R⁵², R⁵³ and R⁵⁴ have the same definitions as defined in the above-described substituents on a ring formed from Q¹ and C. Preferable examples of the pyrrolotriazole-based couplers represented by the general formulae (9) to (12) may include couplers in which at least one of R⁵² and R⁵³ is an electron attractive group described in EP Nos. 488,248A1, 491,197A1, 545,300 and U.S. Patent No. 5,384,236.
In the general formulae (1) to (12), Y³ is a group which imparts diffusion resistance to a coupler and can be released by a coupling reaction with an oxidized product of a developing agent. Examples of Y include a heterocyclic group (a 5 to 7 membered saturated or unsaturated monocyclic or condensed ring having at least one hetero atom such as nitrogen, oxygen, sulfur and the like, examples thereof include succinimide, maleinimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzoimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiozolidine-2,4-dione, imidazolidine-2-one, oxazolidine-2-one, thiazoline-2-one, benzoimidazoline-2-one, benzooxazoline-2-one, benzothiazoline-2-one, 2-pyrroline-5-one, 2-imidazoline-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine and 2-imino-1,3,4-thiazolidine-4-one), a halogen atom (such as chlorine and bromine atoms), an aryloxy group (such as phenoxy and 1-naphthoxy groups), a heterocyclicoxy group (such as pyridyloxy and pyrazolyloxy groups), an acyloxy group (such as acetoxy and benzoyloxy groups), an alkoxy group (such as methoxy and dodecyloxy groups), a carbamoyloxy group (such as N,N-diethylcarbamoyloxy and morpholinocarbonyloxy groups), an aryloxycarbonyloxy group (such as a phenoxycarbonyloxy group), an alkoxycarbonyloxy group (such as methoxycarbonyloxy, and ethoxycarbonyloxy groups), an arylthio group (such as phenylthio and naphthylthio groups), a heterocyclic thio group (such as tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxadiazolylthio and benzoimidazolylthio groups), an alkylthio group (such as methylthio, octylthio and hexadecylthio groups), an alkylsulfonyloxy group (such as a methanesulfonyloxy group), an arylxulfonyloxy group (such as benzenesulfonyloxy and toluenesulfonyloxy groups), a carbonamide group (such as acetamide and trifluoroacetamide groups), a sulfonamide group (such as methanesulfonamide and benzenesulfonamide groups), an alkylsulfonyl group (such as a methanesulfonyl group), an arylsulfonyl group (such as a benzenesulfonyl group), an alkylsulfinyl group (such as a methanesulfinyl group), an arylsulfinyl group (such as a benzenesulfinyl group), an arylazo group (such as phenylazo, naphthylazo groups) and a carbamoylamino group (such as a N-methylcarbamoylamino group).
Y³ may be substituted with a substituent, and examples of the substituent for Y³ include the examples of the substituent on a ring formed from Q¹ and C. The total number of carbon atoms contained in Y³ is preferably from 6 to 50, more preferably from 8 to 40, and most preferably from 10 to 30.
Y³ is preferably an aryloxy, heterocyclicoxy, acyloxy, aryloxycarbonyloxy, alkoxycarbonyloxy or carbamoyloxy group.
In addition to the above-described couplers, couplers having a different structure can be used such as condensed ring phenol-based couplers, imidazole-based couplers, pyrrole-based couplers, 3-hydroxypyridine-based couplers, active methylene, active methine-based couplers, 5,5-condensed ring heterocyclic-based couplers and 5,6-condensed ring heterocyclic-based couplers.
As the condensed phenol-based coupler, couplers described in U.S. patent Nos. 4, 327, 173, 4,564,586 and 4,904,575 can be used.
As the imidazole-based coupler, described in U.S. patent Nos. 4,818,672 and 5,051,347 can be used couplers.
As the 3-hydroxypyridine-based coupler, couplers described in Japanese Patent Application Laid-Open (JP-A) No. 1-315736 can be used.
As the active methylene and active methine-based coupler, couplers described in U.S. patent Nos. 5,104,783 and 5,162,196 can be used.
As the 5,5-condensed ring heterocyclic-based couplers, pyrrolopyrazole-based couplers described in U.S. patent No. 5,164,289 and pyrroloimidazole-based couplers described in JP-A No. 4-174429 can be used.
As the 5,6-condensed ring heterocyclic-based couplers, pyrazolopyrimidine-based couplers described in U.S. patent No. 4,950,585, pyrrolotriazine-based couplers described in JP-A No. 4-204730 and couplers described in EP No. 556,700 can be used.
In the present invention, in addition to the above-described couplers, there can be used couplers described in German Patent Nos. 3,819,051A, 3,823,049, U.S. patent Nos. 4,840,883, 5,024,930, 5,051,347, 4,481,268, EP Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, Japanese Patent Application Laid-Open (JP-A) Nos. 63-141055, 64-32260, 64-32261, 2-297547, 2-44340, 2-110555, 3-7938, 3-160440, 3-172839, 4-172447, 4-179949, 4-182645, 4-184437, 4-188138, 4-188139, 4-194847,4-204532, 4-204731 and 4-204732.
In the coupler used in the present invention, the total number of carbon atoms in parts other than Y³ is preferably from 1 to 30, more preferably from 1 to 24, and most preferably from 1 to 18.
Specific examples of the coupler which can be used in the present invention include, but are not limited to, the following couplers.
The amount added of the coupler used in the present invention depends on the molar absorptivity (ε) of the dye produced, and in the case of a coupler in which ε of a dye produced by coupling is from about 5,000 to 500,000, it is suitable that the amount coated is from about: 0.001 to 100 mmol/m², preferably from about 0.01 to 10 millimol/m², and more preferably from about 0.05 to 5.0 millimol/m², in order to obtain an image density of 1.0 or more in terms of reflection density.
The amount added of the color developing agent used in the present invention represented by the general formulae (I) or (D) is from 0. 01 to 100 times, preferably from 1 to 10 times and more preferably from 0.2 2 to 5 times the amount of the coupler. Further, 2 or more couplers may be used in combination.
Next, compounds represented by the general formulae (II-a), (II-b), (IV-a), (IV-b), (IV-c), (IV-d), (IV-e), (IV-f) and (IV-g) are described below in detail. In general formulae (II-a) and (II-b), R¹ represents a substituted or unsubstituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an amino group, or a heterocyclic group. Preferable examples of R¹ include a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, e. g., a methyl group, an ethyl group and a dodecyl group; a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, e. g., a cyclohexyl group; a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, e. g., a benzyl group and a β-phenetyl group; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e. g., a phenetyl group, a naphthyl group, a tolyl group and a xylyl group; a substituted or unsubstaituted amino group having 0 to 30 carbon atoms, e.g., an amino group, a methylamino group, an isopropylamino group, a cyclohexylamino group, a phenylamino group, a benzylamino group, an N,N-dimethylamino group, an N-methyl-N-ethylamino group, an N,N-diisopropylamino group, an N,N-dicyclohexylamino group, an N,N-diphenylamino group, an N,N-dibenzylamino group; a substituted or unsubstituted heterocyclic ring, e. g., a pyridyl group, a furyl group and a thienyl group.
Examples of the substituents of the aryl group include a halogen atom (such as chlorine and bromine atoms), an amino group, an alkoxy group, an aryloxy group, a carbonamide group, an alkanoyloxy group, a benzoyloxy group, an ureido group, a carbamate group, a carbamoyl group, a carbonate group, a carboxy group, an alkyl group (such as methyl, ethyl and propyl groups), an acylamino group, a sulfamoyl group, an ester group, an alkylsulfonyl group, an alkylsulfonylamino group and an arylsulfonylamino group.
R² represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group.
Preferably example of R² include a hydrogen atom; a halogen atom, e. g., bromine and chlorine; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, e. g., a methyl group, an ethyl group, an isopropyl group and a t-butyl group; a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, e. g., a cyclopentyl group and a cyclohexyl group; a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, e. g., a benzyl group and a β-phenetyl group; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, e. g., a phenyl group and a naphthyl group which are listed for R¹ ; a substituted or unsubstituted heterocyclic group, e. g., a pyridyl group, a furyl group and a thienyl group; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, e. g., a methoxy group, a butoxy group and a methoxyethoxy group; a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, e. g., a phenoxy group; a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, e. g., an acetyl group and a palmitoyl group; a substituted or unsubstituted alkyloxycarbonyl group having 1 to 20 carbon atoms, e. g., a methoxycarbonyl group; an aryloxycarbonyl group having 1 to 20 carbon atoms, e. g., a phenoxycarbonyl group; a substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms, e. g., a methylcarbamoyl group, a dimethylcarbamoyl group and a diisopropylcarbamoyl group; a substituted or unsubstituted sulfamoyl group having 1 to 20 carbon atoms, e. g., a dimethylsulfamoyl group; a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, e. g., a methylsulfonyl group; a substituted or unsubstituted arylsulfonyl group having 1 to 20 carbon atoms, e. g., a phenylsulfonyl group and a p-methyphenylsulfonyl group; a substituted or unsubstituted acylamino group having 2 to 20 carbon atoms, e. g., an acetylamino group, an N-methylacetylamino group and a palmitoylamino group; a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, e. g., a methylthio group and an ethylthio group; a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, e. g., a phenylthio group and an m-methoxycarbonylphenylthio group.
n represents an integer from 0 to 5, and when n is from 2 to 5, R² may be the same or different, or may be linked to form a ring.
As such a ring, bicyclo[2,2,1]hept-2-en, cyclohexene condensed to a benzene ring which is completed by Y described later, are listed.
Ball represents an organic ballasting group which can convert the compound represented by the formula described above into a non-diffusive compound. When R¹ is non-diffusive, Ball is not be required.
The properties of the ballasting group (Ball) are not critical provided that this ballasting group imparts diffusion resistance to this compound. General ballasting groups include a linear or branched alkyl group which is directly or indirectly linked to this compound, and a benzene type or naphthalene type aromatic group which is indirectly or directly linked to a benzene nucleus. An effective ballasting group is a group generally having at least 8 carbon atoms.
Examples thereof include a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms, an acylamino group having 8 to 30 carbon atoms, an acyl group having 8 to 30 carbon atoms, an acyloxy group having 8 to 30 carbon atoms, an alkoxy group having 8 to 22 carbon atoms, an alkylthio group having 8 to 30 carbon atoms and an alkoxy group having an alkoxycarbonyl group having 8 to 30 carbon atoms. Further, as the group which is indirectly linked, those linked via a carbamoyl group or sulfamoyl group (a nitrogen atom in these groups is linked to the ballasting group) represented by the general formulae (V) and (VI) are preferable.
In the general formulae (V) and (VI), R³ is preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms (e. g., a methyl group and an ethyl group), a cycloalkyl group (e. g., a cyclohexyl group) or an aryl group (e. g., a phenyl group).
L represents a bivalent group (e. g., an alkylene group, a phenyl group and a bivalent arylthio group), and m represents 0 or 1.
Y¹ represents an atom group which is required to complete a benzene nucleus or naphthalene nucleus. When Y¹ is an atom group which is required to complete a naphthalene nucleus, Ball and R² can be linked to any ring completed in such a manner.
Specific examples of the compounds represented by the general formulae (II-a) and (II-b) include, but are not limited to, the following compounds.
Next, the general formulae (IV-a) to (IV-g) are explained below. In the general formula (IV-a), A represents an electron attracting group represented by the following formula.
In R²¹ to R²⁹, Q¹, Q² and Y², R^'24, Ra, Rb in the general formulae (IV-a) to (IV-g), the alkyl group represents a linear or branched alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group and a cycloalkenyl group; the alkyl group represents a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group and a naphthyl group; the alkoxy group represents a methoxy group, an ethoxy group, a benzyloxy group, a heterodecyl group and an octadecyl group; the aryloxy group represents a phenoxy group, a 2-methylphenoxy group and a naphthoxy group; the alkyl group represents a methylamino group, a butylamino group and an octylamino group; the anilino group represents a phenylamino group, a 2-chloroanilino group and a 3-dodecyloxycarbonylanilino group; the phenylsulfonyl group represents a 4-tetradecanesulfamoylphenylsulfonyl group; the acyl group represents a tetradecanecarboxylic acid; the alkylene group represents a methylene group, an ethylene group, a 1,10-decylene group and a -CH₂CH₂OCH₂CH₂- group; the arylene group represents a 1,4-phenylene group, a 1,3-phenylene group, a 1,4-naphthylene group and a 1,5-naphthylene group; the aralkylene group represents

; the heterocyclic group represents a pyrazoyl group, an imidazolyl group, a triazolyl group, a pyridyl group, a quinolyl group, a pyperidyl group and a triazinyl group.
Further, examples of the substituent in the substituted alkyl group, substituted aryl group, substituted alkoxy group, substituted aryloxy group, substituted alkylamino group, substituted anilino group, substituted phenylsulfonyl group, substituted acyl group, substituted alkylene group, substituted arylene group, substituted aralkylene group and substituted heterocyclic group in R²¹ to R²⁹, Q¹, Q² and Y², R'²⁴, Ra, Rb, include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, an ureido group, an imide group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
Further, the heterocyclic group in Q² in the general formula (IV-a) and in P in the general formula (IV-f) has the same definitions as defined in the above-described heterocyclic group, and may have the above-described substituent.
In the compounds represented by the general formulae (IV-a) to (IV-g), compounds represented by the general formulae (IV-a), (IV-b) and (IV-d) are preferable, and compounds represented by the general formula (IV-d) are more preferable.
Specific examples of the compounds represented by the general formulae (IV-a) to (IV-g) include, but are not limited to, the following compounds.

(C₄H₉OCH₂CH₂O)₃P=0

C₁₈H₃₇OH C₁₂H₂₅OH C₁₀H₂₁O(CH₂)₅O(CH₂)₂OH
In the present invention, the compounds represented by the general formulae (II-a) to (IV-g) may be used alone or in combinations of two or more. And the compounds can be contained in any of an emulsion layer, an intermediate layer and a protective layer in the photosensitive material, and preferably they are contained in the same layer as that containing the compound represented by the general formula (I) or the coupler. In the present invention, the amount used of the compound represented by the general formulae (II-a) to (IV-g) is preferably in the range from 0.001 to 1000 times by mol, and more preferably from 0.01 to 100 times by mol based on the compound represented by the general formula (I). In the present invention, the compound represented by the general formulae (I) to (IV-g) can be added by the addition method for a hydrophilic compound described below, or added directly after dissolving in a soluble solvent.
Further, in the present invention, the compound represented by the general formulae (II-a) to (IV-g) can also be used as a precursor. The precursor is a compound which does not exhibit a developing action during storage of a photosensitive material, and can not release the compound until influenced by a suitable activator (for example, a base and nucleophilic agent) or heat. The details thereof are described in Japanese Patent Application Laid-Open (JP-A) No. 64-13456.
When the developing agent is a compound represented by the general formula (D), compounds represented by the general formulae (II-a) or (II-b) are preferred as the auxiliary developing agent to be used together with the developing agent.
Next, techniques preferably used together with the present invention are described below.
The heat developing color photosensitive material used in the present invention basically comprises a substrate carrying thereon a photosensitive silver halide emulsion and a binder, and optionally, can contain an organic metal salt oxidizing agent and a dye donating compound (a reducing agent may also act as this compound as described later).
Though these components are added into the same layer in many cases, they can also be divided and added to separate layers. For example, when a dye donating compound which has been colored is contained in a lower layer of a silver halide emulsion, lowering of sensitivity is prevented.
Though it is preferable that the reducing agent is originally contained in the heat developing photosensitive material, it may also be supplied from outside by means such as diffusion from a dye fixing element as described below.
To obtain a wide range of colors on a chromaticity chart using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers each having light-sensitivity in a different spectral range are combined for use. Examples thereof include a combination of a blue sensitive layer, a green sensitive layer, and a red sensitive layer; a combination of a green sensitive layer, a red sensitive layer, and an infrared sensitive layer; a combination of a red sensitive layer, an infrared photosensitive layer (1), and an infrared photosensitive layer (2) as described in Japanese Patent Application Laid-Open (JP-A) Nos. 59-180,550, 64-13,546, 62-253,159 and EP-A 479,167. Each light-sensitive layer can adopt the various arranging orders known in usual color light-sensitive materials. These light-sensitive layers may each be optionally separated into two or more layers as described in Japanese Patent Application Laid-Open (JP-A) No. 1-252,954. In the heat developing photosensitive material, various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer and an anti-halation layer may be provided between the above-described silver halide emulsion layers and also as the top-most layer and bottom-most layer. And various auxiliary layers such as a backing layer and the like can be provided on the opposite side to the substrate. Specifically, the layer structures and combinations thereof of the above-described patents can be provided, namely an undercoat layer as described in U.S. Patent No. 5,051,335, an intermediate layer having a solid pigment as described in Japanese Patent Application Laid-Open (JP-A) Nos. 1-167,838, 61-20,943, an intermediate layer having a reducing agent and DIR compound as described in Japanese Patent Application Laid-Open (JP-A) Nos. 1-129,553, 5-34,884, 2-64,634, an intermediate layer having an electron transferring agent as described in U.S. Patent Nos. 5,017,454, 5,139,919, Japanese Patent Application Laid-Open (JP-A) No. 2-235,044, a protective layer having a reducing agent as described in Japanese Patent Application Laid-Open (JP-A) No. 4-249,245. The substrate is preferably designed so that it has anti-electrostatic properties and the surface resistivity is 10¹² Ω•cm or less.
Next, the silver halide emulsion used in the heat developing photosensitive material is described below in detail. The silver halide emulsion which can be used in the present invention may be any of silver chloride, silver bromide, silver iodo bromide, silver chloro bromide, silver chloroiodide and silver chloroiodo bromide.
The silver halide emulsion used in the present invention may be a surface latent image-type emulsion or also an inner latent image-type emulsion. The above-described inner latent image-type emulsion is combined with a nuclear forming agent and a light fogging agent and used as a direct reversal emulsion. Also, a so-called core-shell emulsion in which inner part of a particle has a different phase from that of the surface part of a particle may be possible, and silver halide having a different composition may be connected by an epitaxial connection. The above-described silver halide emulsion may be a mono dispersion or a multi dispersion type, and preferably used is a method in which mono dispersion emulsions are mixed and gradation is controlled as described in Japanese Patent Application Laid-Open (JP-A) Nos. 1-167,743 and 4-223,463. The particle size is from 0.1 to 2 µm, and from 0.2 to 1.5 µm is particularly preferable. The crystal habit of the silver halide particle may be any of one comprising regular crystals such as a cube, an octahedron, or a tetradecahedron, one comprising an irregular crystal system such as a spherical system, or a tabular system having a high aspect ratio, or one comprising crystal defects such as twin crystal surfaces, or complex systems thereof.
Specifically, any silver halide emulsion prepared by using a method described in U.S. Patent No. 4,500,626, column 50, U.S. Patent No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,029 (1978), RD No. 17,643 (December 1978), pp. 22-23, RD No. 18,716 (November 1979), p. 648, RD No. 307,105 (November 1989), pp. 863-865, Japanese Patent Application Laid-Open (JP-A) Nos. 62-253,159, 64-13,546, 2-236,546 and 3-110,555, P. Glafkides, Chemie et Phisique Photographique, Paul Montel, 1967, G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, 1966, and V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964 can be used.
In the process for preparing the light-sensitive silver halide emulsion used in the present invention, it is preferable that a desalting, process be conducted in order to remove excessive salt. For the desalt, employable methods include a noodle water-washing method in which gelatin is subjected to gelation, and a flocculation method which utilizes an inorganic salt comprising a polyvalent anion (e.g., sodium sulfate), an anionic surfactant, an anionic polymer (e.g., polystyrene sulfonic acid sodium salt) or a gelatin derivative (e.g., aliphatic-acylated gelation, aromatic-acylated gelatin and aromatic-carbamoylated gelatin). A flocculation method is preferably used.
For a variety of purposes, the light-sensitive silver halide emulsion in the present invention may contain a heavy metal such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium. These compounds may be used alone or in a combination or two or more of them. Although the amount added of such compounds varies depending on the purpose of use, this amount is generally in the range of 10^-9 to 10^-3 mol based on 1 mol of silver halide. The heavy metal may be present uniformly in a silver halide grain or may be present in a localized manner within or on the surface of a silver halide grain. Preferred examples of these emulsions are the emulsions described in Japanese Patent Application Laid-Open (JP-A) Nos. 2-236,542, 1-116,637 and Japanese Patent Application No. 4-126,629.
Such compounds as rhodanate, ammonia, a tetra-substituted thioether compound, an organic thioether derivative described in Japanese Patent Application Publication (JP-B) No. 47-11,386, and a sulfur-containing compound described in Japanese Patent Application Laid-Open (JP-A) No. 53-144,319 may be used as a solvent for silver halide in the grain forming stage for the light-sensitive silver halide emulsion used in the present invention.
For other conditions for the silver halide grain formation, reference will be made, e. g., to P. Glafkides, Chemie et Phisique Photographique, Paul Montel, 1967, G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, 1966 and V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964. That is, an employable method may be selected from an acidic method, a neutral method and an ammonia method. Further, any method selected from a single jet method, a double jet method and a combination thereof may be used as a method for reacting a soluble silver salt with a soluble halide. A double jet method is preferable for obtaining a monodisperse emulsion.
A reversed mixing method in which grains are formed in the presence of an excess of silver iron can also be employed. A so-called controlled double jet method in which pAg of the liquid phase for the formation of silver halide is kept constant can also be employed as the double jet method.
Meanwhile, the concentrations, amounts to be added and adding rates of the silver salt and halogen salt may be increased in order to accelerate the growth of the grains (Japanese Patent Application Laid-Open (JP-A) Nos. 55-142,329 and 55-158,124 and U.S. Patent No. 3,650,757.
The stirring of the reaction mixture may be effected by any known method. Further, the temperature and pH of the reaction mixture during the formation of silver halide grains may be selected depending on the desired outcome. The pH is preferably in the range of 2.2 to 8.5, and more preferably 2.5 to 7.5.
A light-sensitive silver halide emulsion is normally a chemically sensitized silver halide emulsion. A sensitizing method by means of chalcogen, such as sulfur sensitization, selenium sensitization or tellurium sensitization, a sensitizing method by means of a rare metal, such as gold, platinum or palladium, and a sensitizing method by means of reduction, which are known sensitizing methods in the preparation of conventional light-sensitive emulsions, may be used alone or in combination thereof as a chemical sensitizing method of the light-sensitive silver halide emulsion used in the present invention (see, for example, JP-A No. 3-110555 and Japanese Patent Application No. 4-75798). A chemical sensitization according any of the above-mentioned methods can be effected in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open (JP-A) No. 62-253159). Moreover, an anti-fogging agent, which is described below, may be added to a silver halide emulsion after the chemical sensitization thereof. More concretely, the methods, which are described in Japanese Patent Application Laid-Open (JP-A) Nos. 5-45833 and 62-40446, can be used.
When a chemical sensitization is carried out, pH is preferably in the range of 5.3 to 10.5, and more preferably 5.5 to 8.5, while pAg is preferably in the range of 6.0 to 10.5, and more preferably 6.8 to 9.0.
The coated weight of the light-sensitive silver halide to be used in the present invention is in the range of 1 mg/m² to 10 g/m², and preferably 10 mg/m² to 10 g/m² based on the weight of the silver.
In order to impart color-sensitivity, such as green-sensitivity, red-sensitivity or infrared-sensitivity, to the light-sensitive silver halide, the light sensitive silver halide emulsion is spectrally sensitized by means of e.g. a methine dye. Further, if necessary, a blue-sensitive emulsion may be spectrally sensitized in order to enhance sensitivity to the light of the blue color region.
Examples of employable dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
More concrete examples of these sensitizing dyes are disclosed, for example, in U.S. Patent No. 4,617,257 and Japanese Patent Application Laid-Open (JP-A) Nos. 59-180550, 64-13546, 5-45828 and 5 - 45834.
Although these sensitizing dyes may be used alone, they may also be used in combinations thereof. A combination of these sensitizing dyes in often used particularly for supersensitization or for adjusting the spectral sensitization wavelength.
The light-sensitive silver halide emulsion used in the present invention may contain a compound which is a dye having no spectral sensitization effect itself together with the sensitizing dye, or a compound substantially incapable of absorbing a visible light but which exhibits a supersensitizing effect (e. g., compounds described in U.S. Patent No. 3,615,641 and Japanese Patent Application Laid-Open (JP-A) No. 63-23145).
The above-mentioned sensitizing dyes can be added to the emulsion at the stage of chemical aging or thereabouts, or before or after the formation of the nucleus of the silver halide grains in accordance with the descriptions in U.S. Patent Nos. 4,183,756 and 4,225,666. These sensitizing dyes or supersensitizers may be added to the emulsion as a solution in an organic solvent such as methanol, as a dispersion such as gelative or as a solution containing a surfactant. The amount to be added is generally in the range of 10^-8 to 10^-2 mol based on 1 mol of silver halide.

Additives used in these processes and known photographic additives, which are used in the heat developing photosensitive material and the pigment fixing material of the present invention, are described in the aforementioned RD No. 17,643, RD No. 18,716 and RD No. 307,105, the relationship in the description is shown below.

Kinds of additives:	RD 17, 643	RD 18,716	RD 307,105
1.	Chemical sensitizer	p. 23	p. 648, RC	p. 866
2.	Sensitivity enhancer	p. 648, RC
3.	Spectral sensitizer/ Supersensitizer	pp. 23-24	pp. 648, RC ~ 649	pp. 866-868
4.	Brightening agent	p. 24	p. 648, RC	p. 868
5.	Anti-fogging agent/ Stabilizer	pp.24-25	p. 649, RC	pp. 868-870
6.	Light absorber/ Filter dye Ultraviolet ray absorber	pp. 25-26	pp. 649, RC ~ 650, LC	p.873
7.	Dye image stabilizer p.	25	p. 650, LC	p. 872
8.	Hardening agent	p. 26	p. 651, LC	pp. 874-875
9.	Binder	p. 26	p. 651, LC	pp. 873-874
10.	Plasticizer/ Lubricant	p. 27	p. 650, RC	p. 876
11.	Coating aid Surfactant	pp. 26-27	p. 650, RC	pp. 875-876
12.	Anti-static agent	p. 27	p. 650, RC	pp. 876-877
13.	Matting agent			pp. 878-879
(RC: right column, LC: left column)

The binder for the structural layers of the heat developing photosensitive material and dye fixing material is preferably a hydrophilic material. Examples thereof may include those described in the aforesaid Research Disclosure and in Japanese Patent Application Laid-Open (JP-A) No. 64-13546, pp. 71-75. More specifically, the binder is preferably a transparent or translucent hydrophilic material, exemplified by a naturally occurring compound, such as a protein including gelatin and a gelatin derivative; and a polysaccharide including a cellulose derivative, starch, gum arabic, dextran and pullulane, and by a synthetic polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, acryl amide polymer. Also usable as the binder is a highly water-absorbent polymer described in U.S. Patent No. 4,960,681 and Japanese Patent Application Laid-Open (JP-A) No. 62-245,260, for example, a homopolymer composed of a vinyl monomer having -COOM or -SO₃M (M stands for a hydrogen atom or an alkali metal), or a copolymer obtained by a combination of these monomers or obtained by a combination of at least one of these monomers and another monomer(s) such as sodium methacrylate and ammonium methacrylate (e. g., SUMIKAGEL L-5H manufactured by Sumitomo Chemical Co., Ltd.). These binders may be used alone or in combinations of two or more. Particularly, a combination of gelatin and any of the above-mentioned non-gelatin binders is preferable. Depending on the desired outcome, a lime-processed gelatin, acid-processed gelatin, and delimed gelatin which has undergone a deliming process to decrease the content of calcium can be used, preferably in combination.
When a system is adopted in which a small amount of water is supplied to effect heat developing, it is possible to absorb water quickly by using the above-described high water-absorbing polymer. Further, apart from the present invention, if a high water-absorbing polymer is used in a dye fixing layer and protective layer thereof, re-transferring of the dye from the dye fixing element to another substance after transfer can be prevented.
In the present invention, the appropriate amount coated of the binder is preferably from 0.2 to 20 g, preferably from 0.2 to 10 g, and more preferably from 0.5 to 7 g per 1 m².
An organic metal salt may be used as an oxidant together with a light-sensitive silver halide in the present invention. Among these organic metal salts, an organic silver salt is particularly preferable.
Examples of the organic compounds which can be used for the preparation of the above-mentioned organic silver salts serving as an oxidant may include benzotriazoles, fatty acids and other compounds described in U.S. Patent No. 4,500,626, columns 52-53. The silver acetylide, which is described in U.S. Patent No. 4,775,613, is also useful. These organic silver salts may also be used in a combination of two or more of them.
The above-mentioned organic silver salt can be used in an amount in the range of 0.01 to 10 mol, and preferably 0.01 to 1 mol, based on 1 mol of the light-sensitive silver halide. The total coated weight of the light-sensitive silver halide and the organic silver salt is in the range of 0.05 to 10 g/m², and preferably 0.1 to 4 g/m², based on the weight of silver.
In the present invention, in addition to the compound represented by the above-described general formulae, known reducing agents can be used together. Further, a dye donating compound having reducing properties as described later is also included (in this case, other reducing agents can also be used together) . Further, a reducing agent precursor, which does not have reducing properties itself but exhibits reducing properties by being influenced. by a nucleophilic agent and heat in a developing process can also be used.
Examples of the reducing agent used in the present invention include reducing agents and reducing agent precursors described in U.S. Patent Nos 4,500,626, columns 49 to 50, 4,839,272, 4,330,617, 4,590,152, 5,017,454, 5,139,919, Japanese Patent Application Laid-Open (JP-A) Nos. 60-140, 335, pp. (17) to (18), 57-40,245, 56-138, 736, 59-178,458, 59-53, 831, 59-182,449, 59-182,450, 60-119,555, 60-128,436, 60-128, 439, 60-198,540, 60-181,742, 61-259,253, 62-201,434, 62-244,044, 62-131,253, 62-131,256, 63-10,151, 64-13, 546, pp. (40) to (57), 1-120,553, 2-32,338, 2-35,451, 2-234,158, 3-160, 443 and EP No. 220,746, pp. 78 to 96.
Combinations of various reducing agents such as those disclosed in U.S. Patent No. 3,039,869 can also be used.
The above-described reducing agents can be used in the intermediate layer and protective layer for various purposes such as prevention of color mixing, improvement in color reproducibility, improvement in the white background and prevention of silver transfer to a dye fixing material. Specific examples of the reducing agent which can be preferably used are described in EP Nos. 524,649, 357,040, Japanese Patent Application Laid-Open (JP-A) Nos. 4-249245, 2-64633, 2-46450 and 63-186240. Also, there can be used reductive compounds which release a development inhibitor described in JP-B No. 3-63733 Japanese Patent Application Laid-Open (JP-A) Nos. 1-150135, 2-110557, 2-64634, 3-43735 and EP No. 451,833.
Further, there can also be adopted an embodiment in which hydroquinone is added to the protective layer described in Japanese Patent Application Laid-Open (JP-A) No. 5-127335.
In the present invention, the total amount added of the reducing agent is from 0.01 to 20 mol, and particularly preferably from 0.1 to 10 mol based on 1 mol of silver.
Hydrophobic additives such as a dye donating compound and a diffusion resistant reducing agent can be introduced into layers of the heat developing photosensitive material according to known methods such as that is described in U.S. Patent No. 2,322,027. In this case, an organic solvent having a high boiling point described in U.S. Patent Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4,599,296, Japanese Patent Application Publication (JP-B) No. 3-62,256 and the like can be optionally used together with an organic solvent having a low boiling point of 50 to 160°C. The dye donating compound, diffusion resistant reducing agent, and organic solvent having a high boiling point can be used in combinations of two or more.
The amount of the organic solvent having a high boiling point is 10 g or less, preferably 5 g or less, and more preferably 1 to 0.1 g per 1 g of the dye donating compound used. Alternatively, it is preferably 1 cc or less, more preferably 0.5 cc or less and most preferably 0.3 cc or less per 1 g of binder.
Further, a diffusion method using a polymer as described in Japanese Patent Application Publication (JP-B) No.51-39853, Japanese Patent Application Laid-Open (JP-A) No. 51-59943, and a method in which a fine particle dispersion thereof is added described in Japanese Patent Application Laid-Open (JP-A) No. 62-30242 can also be used.
In the case of a compound which is substantially insoluble in water, a fine particle thereof can be dispersed and included in a binder in addition to the above-described methods.
When the hydrophobic compound is dispersed in a hydrophilic colloid, various surfactants can be used. For example, there can be used surfactants described in Japanese Patent Application Laid-Open (JP-A) No. 59-157636, pp. (37) to (38) and the above-described Research Disclosure.
In the heat developing photosensitive material used in the present invention, a compound which can realize stabilization of an image at the same time as activating development can be used. Specific compounds which are preferably used are described in U.S. Patent No. 4,500,626, pp. 51 to 52.
In a system which forms an image by diffusive transferring of a dye, various compounds can be added to the structural layers of the heat developing photosensitive material used in the present invention for the purpose of fixing or de-coloring of unnecessary dyes and coloring materials and improvement in the white background of the resulting image.
Specifically, compounds described in EP No. 353,741, 461,416, Japanese Patent Application Laid-Open (JP-A) Nos. 63-163,345 and 62-203,158 can be used.
In the structural layers of the heat developing photosensitive material used in the present invention, various pigments and dyes can be used for the purpose of improving color discrimination and making the material even more highly sensitive.
Specifically, there can be used compounds described in the above-described Research Disclosure, and compounds and layer constructions described in EP-A No. 479,167, 502,508, JP-A Nos. 1-167,838, 4-343,355, 2-168,252, 61-20,943, EP-A No. 479, 167, 502, 508.
In the present invention, a dye fixing material is used together with the heat developing photosensitive material to form an image by diffusion transfer of a dye. The dye fixing material may be coated on a substrate other than that coated with the photosensitive material, or may be coated on the same substrate on which the photosensitive material is coated. The relation between the photosensitive material and the dye fixing material, the relation between the photosensitive material and the substrate, and the relation between the photosensitive material and the white reflective layer are described in U.S. Patent No. 4,500,626, column 57, and can also be applied to the present invention.
The dye fixing material preferably used in the present invention has at least one layer containing a mordanting agent and a binder. As the mordanting agent, an agent known in the photography field can be used, and specific examples thereof include mordanting agents described in U.S. Patent No. 4,500,626, column 58 to 59, Japanese Patent Application Laid-Open (JP-A) Nos. 61-88,256, pp. (32) to (41) and 1-161,236, pp. (4) to (7), mordanting agents described in U.S. Patent No. 4,774,162, 4,619,883 and 4,594,308. Further, dye receptive polymer compounds described in U.S. Patent No. 4,463,079 may also be used.
The binder used in the dye fixing material used in the present invention is preferably the above-described hydrophilic binder. Further, carageenans described in EP No. 443,529 can be preferably used, and latexes having a glass transition temperature of 40°C or less described in Japanese Patent Application Publication (JP-B) No. 3-74,820 can preferably be used.
Auxiliary layers such as protective layers, peeling layers, undercoat layers, intermediate layers, backing layers and curl prevention layers can be provided in the dye fixing material where necessary. It is particularly useful to provide a protective layer.
In the structural layers of the heat developing photosensitive material and dye fixing material, there can be used a plasticizer and lubricant, or an organic solvent having a high boiling point as a peeling improving agent between the photosensitive layer and the dye fixing material. Concrete examples thereof are described in the above-described Research Disclosure, JP-A No. 62-245,253.
Further, for the above-described objective, various silicone oils (all silicone oils including dimethyl silicone oil and modified silicone oil obtained by introducing various organic groups into dimethylsiloxane) can be used. Effective examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical data P6-18B published by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (X-22-3710).
Further, silicone oil described in Japanese Patent Application Laid-Open (JP-A) Nos. 62-215953 and 63-46449 is also effective.
A brightening agent may also be used in the heat developing photosensitive material and dye fixing material. It is preferable that the brightening agent is originally contained inside the dye fixing material, or it is supplied from outside through the heat developing photosensitive material or transfer solvent. Examples thereof may include compounds described in K. Veenkataraman, "The Chemistry of Synthetic Dyes", vol. V, chapter 8, JP-A No. 61-143752. More specific examples thereof include stylbene-based compounds, cumarine-based compounds, biphenyl-based compounds, benzooxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds and carbostylyl-based compounds.
The brightening agent can be used in combination with a fading inhibitor and an ultraviolet ray absorber.
Specific examples of the fading inhibitor, ultraviolet ray absorber, and brightening agent are described in JP-A Nos. 62-215,272, pp. (125) to (137) and 1-161,236, pp. (17) to (43).
Examples of the hardening agent used in the structural layers of the heat developing photosensitive material and dye fixing material may include those described in the above-described Research Disclosures, U.S. Patent Nos. 4,678,739, column 41 and 4,791,042, and in Japanese Patent Application Laid-Open (JP-A) Nos. 59-116655, 62-245261, 61-18942 and 4-218044. More specifically, examples of these hardeners may include an aldehyde (e.g., formaldehyde), an aziridine, an epoxy, a vinylsulfone (e.g., N,N'-ethylene-bis(vinylsulfonylacetamide)ethane), a N-methylol compound (e.g., dimethylolurea) and a polymeric compound (e.g., a compound described in Japanese Patent Application Laid-Open (JP-A) No. 62-234,157).
The amount of the hardener added may be in the range of 0.001 g to, 1 g, and preferably 0.005 to 0.5 g, based on 1 g of coated gelatin. Further, the layer to which the hardener is added may be any of the structural layers of a light-sensitive material and dye fixing material, and also may be separated into two or more layers before addition of the hardener.
The structural layers of the heat developing photosensitive material and dye fixing material may contain various anti-fogging agents or photographic stabilizers or precursors thereof. Specific examples thereof include azole and azaindenes described in RD 17643 (1978), pp. 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in Japanese Patent Application Laid-Open (JP-A) No. 59-168,442, mercapto compounds and metal salts thereof described in Japanese Patent Application Laid-Open (JP-A) No. 59-111636 and acetylene compounds described in Japanese Patent Application Laid-Open (JP-A) No. 62-87957. In the present invention, when a precursor is used, it is preferably contained in the photosensitive silver halide emulsion layer as described above, and can also used in the dye fixing material.
When the compound is not: a precursor, the amount of the compound added may be preferably in the range of 5 × 10^-6 to 1 × 10^-1 mol, and more preferably 1 × 10^-5 to 1 × 10^-2 mol, based on 1 mol of silver. In the case of a precursor, the amount more preferably used is as described above.
For purposes such as improving the coatability, improving peeling, improving lubrication, preventing electrostatic charges and accelerating the developing reaction, various surfactants may be added to the structural layers of the heat developing photosensitive material and dye fixing material. Specific examples of the surfactants include those described in the above-described Research Disclosure, Japanese Patent Application Laid-Open (JP-A) Nos. 62-173,463 and 62-183,457.
For purposes such as improving lubrication, preventing electrostatic charges and improving peeling, an organic fluorine-containing compound may be added to the structural layers of the heat developing photosensitive material and dye fixing material. Typical examples of organic fluorine-containing compounds include a fluorine-containing surfactant, a hydrophobic fluorine-containing compound, such as an oily fluorine-containing compound, e.g., fluorocarbon oil, and a solid fluorine-containing resin, e.g., tetrafluoroethylene, described in Japanese Patent Application Publication (JP-B) No. 57-9053, column 8-17, Japanese Patent Application Laid-Open (JP-A) Nos. 61-20944 and 62-135826.
For purposes such as preventing adhesion and improving lubrication, a matting agent can be used in the heat developing photosensitive material and dye fixing material. Examples of the matting agent may include compounds described in Japanese Patent Application Laid-Open (JP-A) Nos. 63-274944 and 63-274952 such as a benzoguanamine resin bead, polycarbonate resin bead and ABS resin bead; in addition to compounds described in Japanese Patent Application Laid-Open (JP-A) No. 61-88256, p. 29 such as silicon dioxide, polyolefin and polymethacrylate. Further, compounds described in the above-described Research Disclosure can be used.
These matting agents can be added, if necessary, not only to the top layer (protective layer) but also to a lower layer.
Further, the structural layers of the heat developing photosensitive material and dye fixing material may contain a heat solvent, a de-foaming agent, an antimicrobial agent and colloidal silica. Specific examples of these additives are described in Japanese Patent Application Laid-Open (JP-A) No. 61-88256, pp. 26 to 32, Japanese Patent Application Laid-Open (JP-A) No. 3-11338 and Japanese Patent Application Publication (JP-B) No. 2-51496.
In the present invention, an image formation accelerator can be used in the heat developing photosensitive material and/or dye fixing material. The image formation accelerator has such functions as promoting a redox reaction of a silver salt oxidizing agent with a reducing agent, promoting reactions such as the formation or decomposition of a dye from the dye donating material or the releasing of a diffusive dye, and promoting the transfer of a dye from the layer of the heat developing photosensitive material to the dye fixing layer, and is classified from the view point of physicochemical functions into a base or base precursor, nucleophilic compound, high boiling point organic solvent (oil), heat solvent, surfactant and compound having mutual action with silver or silver ion. Since these compounds have generally complex functions, they usually have several of the functions described above in combination. The details thereof are described in U.S. patent No. 4,678,739, pp. 38 to 40.
Examples of the base precursor include a salt of a base and an organic acid which is de-carbonated by heating, a compound which releases amines by intramolecular nucleophilic substitution reaction, Lossen transformation or Beckmann transformation. Specific examples thereof are described in U.S. Patent Nos. 4,514,493, 4,657,848.
In a system in which heat development and transfer of a dye are conducted simultaneously in the presence of a small amount of water, a method in which a base and/or base precursor is contained in the dye fixing material is preferable from the view point of increasing in preservability of the heat developing photosensitive material.
In addition to the above-described methods, a combination of a poor-soluble metal compound with a compound (complex forming compound) which can effect a complex forming reaction with a metal ion constituting this poor-soluble metal compound, described in EP No. 210,660 and U.S. Patent No. 4,740,445 and a compound which generates a base by electrolysis described in Japanese Patent Application Laid-Open (JP-A) No. 61-232451 can also be used as the base precursor. The former method is particularly effective. It is advantageous that the poor-soluble metal compound and complex forming compound are added separately to the heat developing photosensitive material and dye fixing material as described in the above-described patents.
In the present invention, various development stopping agents can be used in the heat developing photosensitive material and/or dye fixing material for the purpose of obtaining a constant image in spite of variations in the processing temperature and processing time during developing.
The development stopping agent is a compound which, at the appropriate stage of development, quickly neutralizes or reacts with a base to decrease the concentration of the base in a film for stopping the development, or which effects a mutual reaction with silver or silver salt to suppress the development. Specific examples thereof include an acid precursor which releases an acid by heating, an electrophilic compound which generates by heating a substitution reaction with a coexisting base, or a nitrogen-containing heterocyclic compound, mercapto compound and precursors thereof. Further details thereof are described in Japanese Patent Application Laid-Open (JP-A) No. 62-253159, pp. (31) to (32).
In the present invention, as the substrate of the heat developing photosensitive material and dye fixing material, a material which can endure the processing temperature can be used. In general, substrates for photography such as paper and synthetic polymer (film) described in Japan Photograph Assosiation's "Base for Photographic Technology (ed. by Silver Salt Photography)" Corona Corp., 1979, pp. (223) to (240), can be listed. Specific examples thereof which can be used include films composed of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, poly vinyl chloride, polystyrene, polypropylene, polyimide or celluloses (for example, triacetylcellulose) or films containing a dye such as titanium oxide, and synthetic paper for films made from polypropylene, mixed paper made from natural pulp, and synthetic resin pulp such as polyethylene, Yankee paper, baryta paper, coated paper (particularly, cast-coated paper), metal, fabrics and glasses.
These may be used alone, or may be used in the form of a substrate of which one side or both sides are laminated with a synthetic polymer such as polyethylene. This laminated layer can optionally contain pigments and dyes such as titanium oxide, ultramarine blue pigment and carbon black.
In addition to these, substrates described in Japanese Patent Application Laid-Open (JP-A) Nos. 62-253159, pp. (29) to (31), 1- 61,236, pp. (14) to (17), 63-316848, 2-22651, 3-56955 and U.S. Patent No. 5,001,033 can be used.
The back surface of this substrate may be coated with a hydrophilic binder and a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents. Specifically, substrates which are described in Japanese Patent Application Laid-Open (JP-A) No. 63 - 220246 can be used. Further, the front surface of the substrate is preferably subjected to various surface processes and under coating for the purpose of improving adhesion with the hydrophilic binder.
For exposure and recording of an image on the heat developing photosensitive material, there are, for example, methods in which scenery and people are directly photographed using a camera, methods in which exposure is effected through a reversal film or negative film using a printer and enlarger, methods in which scanning exposure of an original image is effected through a slit using an exposing apparatus of a copy machine, a method in which light emission is effected from an emission diode and various lasers (laser diode, gas laser) via electric signals and scanning exposure is conducted on an image information (methods described in Japanese Patent Application Laid-Open (JP-A) Nos. No. 2-129625, 5176144, 5-199372, 6-127021), methods in which image information is outputted on an image display apparatus such as a CRT, a liquid crystal display, an electroluminescent display and a plasma display, and exposure is effected directly or with an optical system.
As the light source for recording an image on the heat developing photosensitive material, there can be used light sources and exposing methods described in U. S. patent No. 4,500,626, column 56, Japanese Patent Application Laid-Open (JP-A) No. 2-53,378 and 2-54,672 such as natural light, a tungsten lamp, a light emitting diode, a laser light source and a CRT light source, as described above.
Further, image exposure can also be conducted using a wavelength converting element which is obtained by combining a non-linear optical material with a coherent light source such as a laser light. The non-linear optical material is a material which can manifest non-linear characteristics between an electric field and the polarization which occurs when a strong light electric field such as from a laser light is imparted, and preferably used are inorganic compounds represented by lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate and BaB₂O₄, urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), compounds described in Japanese Patent Application Laid-Open (JP-A) Nos. 61-53462 and 62-210432. Various forms of the wavelength converting element, such as a monocrystalline light directing route type and a fiber type are known, and all of them are effective.
Further, the above-described image information can utilize image signals obtained from a video camera and an electronic still camera, television signals represented by that stipulated by Nippon Television Signal Criteria (NTSC), image signals obtained by dividing an original image into many picture elements such as that obtained from a scanner, and image signals made by a computer represented by CG, CAD.
The heat developing photosensitive material and/or dye fixing material used in the present invention may adopt a form having an electroconductive heat generating layer as a heating means for heat developing and diffusion transferring of a dye. As the heat generating element in this case, one from those described in Japanese Patent Application Laid-Open (JP-A) No. 61-145544 can be used.
The heating temperature in the heat developing is from 50 to 250°C, and a temperature from 60 to 180°C is particularly useful. The diffusion transfer process of a dye may be conducted simultaneously with the heat development or may be conducted after the completion of the heat development process. In the latter case, it is particularly preferable that the heating temperature in the transfer process is 50°C or higher, and about 10°C lower than the temperature during the heat developing process, although the transfer process can be conducted at between room temperature to the temperature in the heat developing process.
Though movement of the dye is caused only by heat, a solvent may be used to promote the dye movement. A method is also useful in which development and transfer are conducted simultaneously or continuously by heating in the presence of a small amount of solvent (especially, water) as described in U.S. Patent Nos. 4,704,345, 4,740,445 and Japanese Paten Application Laid-Open (JP-A) No. 61-238,056. In this method, the heating temperature is preferably 50°C or higher and not more than boiling point of the solvent. For example, when the solvent is water, it is preferably from 50 to 100°C.
Examples of the solvents used for promoting the development and/or the diffusion transfer of a dye include water, an aqueous basic solution containing an inorganic alkaline metal salt and an organic base (as these bases, those described in the column of the image formation promoter can be used), solvents having a low boiling point, or a mixture of solvents having a low boiling point and water or the above-described aqueous basic solution. Further, the solvent may contain a surfactant, an anti-fogging agent, a compound which forms a complex with a poor-soluble metal salt, an antifungal agent and, an antimicrobial agent.
As the solvent used in these heat developing and diffusion transfer processes, water is preferably used, and any water usually used may be used. Specifically, distilled water, tap water, well water and mineral water can be used. Further, in a heat developing apparatus using the heat developing photosensitive material and dye fixing material used in the present invention, water may be used without recycling or may be recycled and used repeatedly. In the latter case, water containing components eluted from material shall be used. Apparatuses and water described in Japanese Paten Application Laid-Open (JP-A) Nos. 63-144354, 63-144355, 62-38460 and 3.21055 may also be used.
These solvents may be added to the heat developing photosensitive material, the dye fixing material or to both of them. The amount used thereof may not be more than the weight of solvent corresponding to the maximum swollen volume of the total coated film.
As this method for imparting water, there are preferably used methods described in Japanese Paten Application Laid-Open (JP-A) No. 62-253159 p. (5), Japanese Paten Application Laid-Open (JP-A) No. 63 - 85544 and Japanese Patent Application No. 8 - 181045. It is also possible that a solvent is enclosed in a micro capsule, or a solvent is previously contained in the heat developing photosensitive material or dye fixing element or both of them in the form of a hydrate.
The temperature of water added may be from 30 to 60°C as described in Japanese Paten Application Laid-Open (JP-A) No. 63-85544. It is particularly useful that the temperature is 45°C or higher for the purpose of preventing proliferation of contaminant bacteria in water.
To promote dye movement, a hydrophilic hot solvent which is solid at ordinary temperature and is dissolved at high temperatures can be contained in the heat developing photosensitive material and/or dye fixing material. The layer which contains the solvent may be any of a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, with dye fixing layer and/or adjacent layer thereof being preferable.
Examples of the hydrophilic hot solvent include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic rings.
Examples of heating methods in the developing and/or transferring processes include contacting with a heated block and plate, contacting with a heat plate, hot pressing, heat rolling, using a heat drum, a halogen lamp heater, infrared and far infrared lamp heaters and passing through a high temperature atmosphere. For laminating the heat developing photosensitive material and dye fixing material, methods described in Japanese Paten Application Laid-Open (JP-A) Nos. 62-253159 and 61-147244 p. (27) can be adopted.
For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For examples, apparatuses described in Japanese Patent Application Laid-Open (JP-A) Nos. 59-75,247, 59-177,547, 59-181,353, 60-18,951, 62-25,944, Japanese Patent Application Nos. 4-277517, 4-243072 and 4-244693 are preferably used. As commercially available apparatuses, PICTOSTAT 100, 200, PICTOGRAPHY 3000 and 2000 manufactured by Fuji Photo Film Co., Ltd., can be used.
When an image obtained from the above-described photosensitive material and dye fixing element is used as a color proof for printing, the method of density expression thereof may be any of a continuous gradation control method, an area gradation control method utilizing parts of discontinuous density, or a gradation control method obtained by combining the first two.
When LD or LED is used as a light source, output of a digital signal is possible. By this, applications in which control of the design and hue of a print is conducted on CRT, and a color proof is outputted as the final output (DDCP) are possible. Namely, DDCP is an effective means for conducting output of a proof efficiently in the field of color proofs. The reason for this is that a color printer has a relatively simple structure and is inexpensive, and by using the color printer, as is well known, production of a preparation film for a color printer and production of a press plate (PS plate) are not necessary, therefore, a hard copy obtained by forming an image on a sheet can be easily produced in a short period of time for several times.
When LD or LED is used as a light source, it is preferable that three spectral sensitivities of yellow, magenta and cyan color forming layers, four spectral sensitivities of yellow, magenta, cyan and black color forming layers, or, for the purpose of obtaining a desirable hue, spectral sensitivities of the respective colors forming layers obtained by mixing two or more dye forming compound, have respective peaks of the spectral sensitivities at separate wavelengths respectively apart by 20 nm or more. Further, as another method, when the spectral sensitivities of two or more different colors differ by 10 times or more, a method in which an image of two or more colors is obtained by one radiation wavelength is also adopted.
Next, a method for reproducing moire and the like of a print using a color printer is described below.
To produce a color proof for printing which correctly reproduces moire appearing on a print of high resolution by a color printer of low resolution, the respective net point area ratio data aj of a CMYK4 size plate are respectively converted to 48800DPI bit map data b'j by referring to a threshold matrix 24. Then, the area ratio ci of each color is counted by referring simultaneously to the bit map data b'j in a given range. Then, the primary three stimulation value data X, Y, Z of 1600DPI, which show the measured value data of the above-described respective colors previously calculated, are calculated. The secondary three stimulation value data X', Y', Z' of 400 DPI are calculated by anti-areazing filter processing of the primary three stimulation value data X, Y, Z. The calculated data are used as input data for the color printer. (This is described in Japanese Patent Application No. 7-5257 in detail.)
When color image recording is conducted using an output apparatus such as a color printer, it is possible, for example, that a color image having desired color is realized by manipulating color signals relating to yellow, and magenta, cyan colors. However, since the color signals depend on the output characteristics of the output apparatus, it is necessary that a color signal supplied from an external apparatus having different characteristics is subjected to color converting processing with consideration given to the above-described output characteristics.
Then, a plurality of known color patches having different colors are produced using the output apparatus, and the colors of the above-described color patches are measured, to obtain, for example, a conversion relation (hereinafter referred to as the orderly conversion relation) in which the known color signals CMY of the above-described color patch are converted to stimulus value signals XYZ which do not depend on the output apparatus, then a conversion relation (hereinafter referred to as a reverse conversion relation) by which the stimulus value signals XYZ are converted to color signals CMY is calculated utilizing the orderly conversion relation, and the above-described color conversion processing is conducted using this reverse conversion relation.
Herein, the following three examples are listed as a method for calculating color signals CMY from the stimulus value signals XYZ, however, the examples of the present invention are not limited to them.
(1) A tetrahedral in which four stimulus value signals XYZ constitute respective summits is established, the space of the stimulus value signals XYZ is divided by this tetrahedron, and the space of color signals CMY is also divided by the tetrahedron in the same manner, and the color signals CMY are calculated by linear computing for any stimulus value signals XYZ in the corresponding tetrahedron.
(2) Color signals CMY are calculated by repeated computing using the Newton method (see, PHOTOGRAPHIC SCIENCE AND ENGINEERING Volume 16, Number 2. March-April 1972 pp136-pp143 "Metameric color matching in subtractive color photography") for any stimulus value signals XYZ.
(3) A color conversion method which converts color signals from the First Color System to the Second Color System, comprising a first step in which the relation of real color signals in First Color System obtained from known real color signals in Second Color System is found as the first orderly conversion relation, a second step in which the hypothesis color signals are set outside the area composed of the real color signals by approximating the first orderly conversion relation using a monotone function, a third step in which the relation of the color signals in First Color System obtained by color signals composed of the real color signals, and the hypothesis color signals in Second Color System is found as the second orderly conversion relation, and a fourth step in which the relation of color signals in the First Color System is found as a reverse conversion relation using a repeated computing method from the second conversion relation, and a color signal is converted from the First Color System to Second Color System using the reverse conversion relation. Namely, by this conversion method which converts color signals from First Color System to Second Color System, real color signals (for example, XYZ color signals) in First Color System corresponding to known real color signals (for example, CMY color signals) in Second Color System are found, then, the first orderly conversion relation between these real color signals is approximated by a monotone function, and hypothesis color signals are set outside the area composed of the real color signals. Then, according to the second orderly conversion relation between First Color System and Second Color System respectively composed of the real color signals and the hypothesis color signals, a reverse conversion relation is found which effects conversion to First Color System and Second Color System by repeated computing represented by the Newton method, and color conversion is conducted using this reverse conversion relation. Further, methods other than this are also listed.
The size of an image obtained from the heat developing photosensitive material and dye fixing element may be any of A line book size, A1 to A6, KIKU line book size (636mm × 939mm), B line book size, B1 to B6, four-six size. The size of the heat developing photosensitive material and dye fixing element may be any size in the width range from 100 mm to 2000 mm, corresponding to the above-described sizes.
For the heat developing photosensitive material and dye fixing element, the materials may be supplied in the form of either a roll or sheet, and it is also possible that only one of them is in the form of roll, and the other is in the form of sheet.

EXAMPLE

The following examples further illustrate the present invention in detail, but do not limit the scope thereof.

Example 1

Image receiving elements R101 having the structures shown in Table 1 and Table 2 were produced.

Structure of image receiving element R101
Number of layer	Additive	Amount applied (mg/m²)
6th layer	Water-soluble polymer (1)	130
Water-soluble polymer (2)	35
Water-soluble polymer (3)	45
Potassium nitrate	20
Anionic surfactant (1)	6
Anionic surfactant (2)	6
Ampholytic surfactant (1)	50
Stain inhibitor (1)	7
Stain inhibitor (2)	12
Matting agent (1)	7
5th layer	Gelatin	250
Water-soluble polymer (1)	25
Anionic surfactant (3)	9
Hardener (1)	185
4th layer	Mordanting agent (1)	1850
Water-soluble polymer (2)	260
Water-soluble polymer (4)	1400
Latex dispersion (1)	600
Anionic surfactant (3)	25
Nonionic surfactant (1)	18
Guanidine picolinate	2550
Sodium quinolinate	350
3rd layer	Gelatin	370
Mordanting agent (1)	300
Anionic surfactant (3)	12
2nd layer	Gelatin	700
Mordanting agent (1)	290
Water-soluble polymer (1)	55
Water-soluble polymer (2)	330
Anionic surfactant (3)	30
Anionic surfactant (4)	7
Organic solvent having a high boiling point (1)	700
2nd layer	Optical brightener (1)	30
Stain inhibitor (3)	32
Guanidine picolinate	360
Potassium quinolinate	45
1st layer	Gelatin	280
Water-soluble polymer (1)	12
Anionic surfactant (1)	14
Sodium m-borate	35
Hardener (1)	185
Substrate (1) Paper substrate laminated with polyethylene (thickness: 215µm)

The amount applied of latex dispersion is the same as the amount applied of latex solid

Organic solvent having a high boiling point (1)
C₂₆H_46.9Cl_7.1
(En-para 40 [manufactured by Ajinomono Co., Inc.])
Water-soluble polymer (1)
SUMIKAGEL L5-H (manufactured by Sumitomo Chemical Co., Ltd.)
Water-soluble polymer (2)
DEXTRAN (molecular weight: 70000)
Water-soluble polymer (3)
κ^- carageenan (manufactured by Taito Corp.)
Water-soluble polymer (4)
MP polymer MP-102 (manufactured by Kuraray Co., Ltd.)
Water-soluble polymer (5)
Acryl-modified copolymer of polyvinyl alcohol (degree of modification: 17%)
Latex dispersion (1)
LX-438 (manufactured by Nippon Xeon Co., Ltd.)
Matting agent (1)
SYLOID79 (manufactured by Fuji Devison Chemical Co., Ltd.)
Matting agent (2)
PMMA particle (average particle size 4µm)

Among these compounds, an oil-soluble compound was dissolved in the organic solvent having a high boiling point (1) and emulsified and dispersed before being added to the composition, and a water-soluble compound or latex was directly added to the composition. Next, a method for producing a photosensitive element is described.
First, a method for producing a photosensitive silver halide emulsion is described.

Photosensitive silver halide emulsion (1) [for red sensitive emulsion layer]

A solution (I) having the composition shown in Table 4 was added to an aqueous solution having the composition shown in Table 3 at a constant flow rate with sufficient stirring over a period of 9 minutes, and a solution (II) was added at a constant flow rate 10 seconds before the addition of the solution (I) over a period of 9 minutes and 10 seconds. 36 minutes after the addition, a solution (III) having the composition shown in Table 4 was added at a constant flow rate over a period of 24 minutes, and a solution (IV) was added at a constant flow rate simultaneously with the solution (III) over a period of 25 minutes.

The mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 880 g of lime-processed ossein gelatin was added to control pH to 6.0 before the addition of 12. 8 g of ribonucleic acid dissociated compound and 32 mg of trimethylthiourea, and the mixture was chemically sensitized for 71 minutes at 60°C, then, 2.6 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 3.2 g of a dye (a), 5.1 g of KBr and 2.6 g o'f a stabilizer described below were added one by one, and the resulting mixture was cooled. In this manner, 28.1 kg of monodispersed cubic silver chloride bromide emulsion having an average particle size of 0.35 µm was obtained.

Composition
H₂O	26300cc
Lime-processed gelatin	800g
KBr	12g
NaCl	80g
Compound (a)	1.2g
Temperature	53°C

	(I) solution	(II) solution	(III) solution	(IV) solution
AgNO₃	1200g	None	2800g	None
KBr	None	546g	None	1766g
NaCl	None	144g	None	96g
K₂IrCl₆	None	3.6mg	None	None
Total amount	Water is added up to 6.5 liter	Water is added up to 6.5 liter	Water is added up to 10 liter	Water is added up to 10 liter

Photosensitive silver halide emulsion (2) [for green sensitive emulsion layer]

Solutions (I) and (II) each having the composition shown in Table 6 were simultaneously added to an aqueous solution having the composition shown in Table 5 at a constant flow rate with sufficient stirring over a period of 9 minutes. 5 minutes after the addition , solutions (III) and (IV) each having the composition shown in Table 6 were simultaneously added at a constant flow rate over a period of 32 minutes. After completion of the addition of the solutions (III) and (IV), 60 ml of a methanol solution of dyes (containing 360 mg of a dye (b1) and 73.4 mg of a dye (b2)) was added at one time.

The mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.6 before addition of 1.8 mg of sodium thiosulfate and 180 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and the mixture was chemically sensitized at 60°C, then 90 mg of an anti-fogging agent (1) were added, and the resulting mixture was cooled. In this manner, 635 g of monodispersed cubic silver chloride bromide emulsion having an average particle size of 0.30 µm was obtained.

Composition
H₂O	600cc
Lime-processed gelatin	20g
KBr	0.3g
NaCl	2g
Compound (a)	0.03g
Sulfuric acid (1N)	16cc
Temperature	46°C

	(I) solution	(II) solution	(III) solution	(IV) solution
AgNO₃	10.0g	None	90.0g	None
KBr	None	3.50g	None	57.1g
NaCl	None	1.72g	None	3.13g
K₂IrCl₆	None	None	None	0.03mg
Total amount	Water is added up to 126 ml	Water is added up to 131 ml	Water is added up to 280 ml	Water is added up to 289 ml

Photosensitive silver halide emulsion (3) [for blue sensitive emulsion layer]

Solutions (I) and (II) each having the composition shown in Table 8 were added to an aqueous solution having a composition as shown in Table 7, in a manner that the solution (II) was added first, and 10 seconds after, the solution (I) was added respectively over a period of 30 minutes with sufficient stirring. 2 minutes after completion of the addition of the (I) solution, a solution (V) was added, and 5 minutes after completion of the addition of the solution (II), a solution (IV) was added over a period of 28 minutes, and 10 seconds after, a solution (III) was added over a period of 27 minutes and 50 seconds.

The mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 1230 g of lime-processed ossein gelatin and 2.8 mg of a compound (b) were added to control pH to 6.1 and pAg to 8.4, before addition of 24.9 mg of sodium thiosulfate, and the mixture was chemically sensitized at 60°C, then, 13.1 g of a dye (c) and 118 ml of a compound (c) were added successively, and the resulting mixture was cooled. The halide particles in the resulted emulsion were potato-like particles, and had an average particle size of 0.53µm, with a yield of 30700 g.

Composition
H₂O	29200cc
Lime-processed gelatin	1582g
KBr	127g
Compound (a)	0.66g
Temperature	72°C

	(I) solution	(II) solution	(III) solution	(IV) solution	(V) solution
AgNO₃	939g	None	3461g	None	None
KBr	None	572g	None	2464g	None
KI	None	None	None	None	22g
Total amount	Water is added up to 6690 ml	Water is added up to 6680 ml	Water is added up to 9700 ml	Water is added up to 9740 ml	Water is added up to 4400 ml

Next, a method for preparing a gelatin dispersion of a hydophobic additive is described.
Gelatin dispersions of yellow coupler (1), magenta coupler (1), cyan coupler (1) and developing agent were prepared respectively according to formulations shown in Table 9. Namely, oil phase components were heated at about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
A gelatin dispersion of an anti-fogging agent (4) was prepared according to the formulation shown in Table 10. Namely, oil phase components were heated at about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.

Organic solvent having a high boiling point (5)
(En-para 40 [manufactured by Ajinomono Co., Inc.]) C₂₆H_48.9Cl_7.1
A dispersion of a polymer latex (a) was prepared according to the formulation shown in Table 11. Namely, to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 1 was added an anionic surfactant (6) over a period of 10 minutes while stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using a ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth.

Dispersion composition

Polymer latex (a) aqueous solution (solid content: 13%) 108ml

Surfactant (5) 20g

Anionic surfactant (6) 600ml

Water 1232ml
A gelatin dispersion of zinc hydroxide was prepared according to a formulation shown in Table 12. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using glass beads having an average particle size of 0.75 mm by a mill. Further, the glass beads were separated and removed, to give a uniform dispersion.

Dispersion composition

Zinc hydroxide 15.9g

Carboxymethylcellulose 0.7g

Sodium polyacrylate 0.07g

Lime-processed gelatin 4.2g

Water 100ml

Preservative (2) 0.4g
Then, a gelatin dispersion of a reducing agent (1) was prepared according to the formulation shown in Table 13. Namely, oil phase components were heated at 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion. Further, ethyl acetate was removed from the resulted dispersion using a vacuum organic solvent removing apparatus.
Next, a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed. Then, methylene chloride was removed by using a vacuum solvent removing apparatus to give a uniform dispersion having an average particle sized of 4.3 µm.

The above-described products were used to produce photosensitive elements 101 shown in Tables 14 and 15.

Structure of main materials of lightsensitive element 101
NO of layer	Name of layer	Additive	Amount added (mg/m²)
7th layer	Protective layer	Acid-processed gelatin	387
	Matting agent (PMMA resin)	17
	Surfactant (2)	6
	Surfactant (3)	20
	Polymer latex (a)
	Dispersion	10
	Reducing agent (1)	47
6th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Water-soluble polymer (1)	5
	Zinc hydroxide	558
	Calcium nitrate	6
5th layer	Blue lightsensitive	layer Lime-processed gelatin	587
	Lightsensitive silver halide emulsion (3)	399
	Yellow dye forming coupler (1)	410
	Developing agent (2)	328
	Anti-fogging agent (3)	15
	Solvent having a high boiling point (4)	433
	Surfactant (1)	12
	Water-soluble polymer (1)	40
4th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Water-soluble polymer (1)	4
	Zinc hydroxide	341
	Calcium nitrate	8

Structure of main materials of lightsensitive element 101 (cont.)
NO of layer	Name of layer	Additive	Amount added (mg/m²)
3rd layer	Green lightsensitive layer	Lime-processed gelatin	452
	Lightsensitive silver halide emulsion (2)	234
	Magenta dye forming coupler (20)	420
	Developing agent (2)	336
	Anti-fogging agent (2)	15
	Solvent having a high boiling point (4)	444
	Surfactant (1)	12
	Water-soluble polymer (1)	10
2nd layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Solvent having a high boiling point (2 )	101
	Solvent having a high boiling point (5	9
	Surfactant (1)	21
	Surfactant (4)	21
	Water-soluble polymer (1)	10
	Calcium nitrate	6
1st layer	Red lightsensitive	layer Lime-processed gelatin	373
	Lightsensitive silver halide emulsion (1)	160
	Cyan dye forming coupler (15)	390
	Developing agent (2)	312
	Anti-fogging agent (2)	14
	Solvent having a high boiling point (4)	412
	Surfactant (1)	11
	Water-soluble polymer (2)	25
	Hardener (1)	45
	Preservative (3)	45
Substrate (substrate obtained by aluminum vapor deposition on a 20 µm PET and subsequent coating of gelatin on the surface as an undercoat)

Hardener (1) CH₂=CHSO₂CH₂SO₂CH=CH₂

Then, photosensitive materials 102 to 115 shown in Table 16 were produced by adding the compound used in the present invention to the 1st, 3rd and 5th layers or the 2nd, 4th and 6th layers, and by changing the coupler and developing agent.
Then, image output was conducted using photosensitive elements 101 to 117 and image receiving element R101 in heating conditions of 80°C for 30 seconds or 75°C for 30 seconds using a PICTOSTAT 330 manufactured by Fuji Photo Film Co., Ltd. The resulting image was a clear color image. {Maximum density and minimum density were measured by a reflection density meter X-lite 304 manufactured by X-lite Corp.}
The discrimination of the resulting image was evaluated by d-value = (Minimum density/Maximum density) (when d value is low, discrimination is excellent).
The results are shown in Table 17. It is understood that the photosensitive element in accordance with the present invention is not easily affected by differences in processing conditions, and can provide an image having an excellent discrimination even under low temperature developing conditions.

Each photosensitive element was left for 5 days under 60°C -60%RH, then image formation was conducted under conditions of 80°C for 30 seconds as described above, and preservability of the photosensitive element was evaluated. The photosensitive element in accordance the present invention provided a clear color image even after preservation.

Lightsensitive element	d value (80 to 30 seconds)	d value (75 to 30 seconds)
101	Y	0.30	Y	0.38
	M	0.20	M	0.30
	Cy	0.18	Cy	0.29
102	Y	0.25	Y	0.27
	M	0.15	M	0.16
	Cy	0.14	Cy	0.17
103	Y	0.24	Y	0.28
	M	0.16	M	0.16
	Cy	0.15	Cy	0.18
104	Y	0.24	Y	0.27
	M	0.16	M	0.17
	Cy	0.15	Cy	0.19
105	Y	0.25	Y	0.28
	M	0.15	M	0.18
	Cy	0.16	Cy	0.19
106	Y	0.24	Y	0.27
	M	0.16	M	0.17
	Cy	0.15	Cy	0.19
107	Y	0.25	Y	0.28
	M	0.15	M	0.16
	Cy	0.16	Cy	0.18
108	Y	0.24	Y	0.26
	M	0.14	M	0.15
	Cy	0.14	Cy	0.17
109	Y	0.33	Y	0.39
	M	0.22	M	0.33
	Cy	0.19	Cy	0.31
110	Y	0.25	Y	0.28
	M	0.15	M	0.18
	Cy	0.16	Cy	0.19
111	Y	0.30	Y	0.38
	M	0.23	M	0.31
	Cy	0.19	Cy	0.22
112	Y	0.24	Y	0.29
	M	0.19	M	0.20
	Cy	0.17	Cy	0.19
113	Y	0.21	Y	0.22
	M	0.11	M	1.14
	Cy	0.10	Cy	0.14
114	Y	0.21	Y	0.23
	M	0.13	M	1.13
	Cy	0.11	Cy	0.13
115	Y	0.21	Y	0.22
	M	0.12	M	1.14
	Cy	0.11	Cy	0.13

Example 2

Image receiving elements were produced in the same manner as in Example 1.
Next, a method for producing a photosensitive element is described.
Firstly, a method for producing a photosensitive silver halide emulsion is described.

Photosensitive silver halide emulsion (1) [emulsion for 5th layer (680 nm photosensitive layer)]

Solutions (I) and (II) each having the composition shown in Table 19 were simultaneously added to an aqueous solution having the composition shown in Table 18 with sufficient stirring over a period of 13 minutes, and 10 minutes after, solutions (III) and (IV) each having the composition shown in Table 19 were added over a period of 33 minutes.

Composition
H₂O	620cc
Lime-processed gelatin	20g
KBr	0.3g
NaCl	2g
Solvent for silver halide (1)	0.03g
Sulfuric acid (1N)	16cc
Temperature	45°C

	(I) solution	(II) solution	(III) solution	(IV) solution
AgNO₃	30.0g	None	70.0g	None
KBr	None	13.7g	None	44.2g
NaCl	None	3.62g	None	2.4g
K₂IrCl₆	None	None	None	0.039mg
Total amount	Water is added up to 126ml	Water is added up to 132ml	Water is added up to 254ml	Water is added up to 252ml

13 minutes after initiation of the addition of the solution (III), 150 cc of an aqueous solution containing 0.350% of a sensitizing dye (1) was added over 27 minutes.
The mixture was washed with water and desalted (conducted at a pH of 4.1 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.9, and the mixture was chemically sensitized at 60°C. The compound used in the chemical sensitization is shown in Table 20.

The resulted emulsion (630 g) was a monodispersed cubic silver chloride bromide emulsion having a variation coefficient of 10.2% and an average particle size of 0.20 µm.

Drug used in chemical sensitization	Amount added
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene	0.36g
Sodium thiosulfate	6.75mg
Anti-fogging agent (1)	0.11g
Preservative (1)	0.07g
Preservative (2)	3.31g

Photosensitive silver halide emulsion (2) [emulsion for 3rd layer (750 nm photosensitive layer)]

Solutions (I) and (II) each having the composition shown in Table 22 were simultaneously added to an aqueous solution having a composition shown in Table 21 with sufficient stirring over a period of 18 minutes. 10 minute after the addition , solutions (III) and (IV) each having the composition shown in Table 22 were added over a period of 24 minutes.

	(I) solution	(II) solution	(III) solution	(IV) solution
AgNO₃	30.0g	None	70.0g	None
KBr	None	13.7g	None	44.2g
NaCl	None	3.62g	None	2.4g
K₄[Fe(CN)₆]·H₂O	None	None	None	0.07g
K₂IrCl₆	None	None	None	0.04mg
Total amount	Water is added up to 188ml up	Water is added to 188ml up	Water is added to 250ml up	Water is added to 250ml

The mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 22 g of lime-processed ossein gelatin which had been subjected to de-calcium processing (calcium content: 150 PPM or less) was added, and the mixture was dispersed at 40°C, and 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to control pH to 5.9 and pAg to 7.8. Then, the mixture was chemically sensitized at 70°C using the chemicals shown in Table 23. Further, at the end of the chemical sensitization, sensitizing dye (2) was added in the form of a methanol solution (the solution having the composition shown in Table 24). Further, after chemical sensitization, the solution was cooled down to 40°C, to this was added 200 g of a gelatin dispersion of a stabilizer (1) described later, and they were sufficiently stirred before being stored. The resulting emulsion was a monodispersion cubic silver chloride iodide having a variation coefficient of 12.6% and an average particle size of 0.25 µm, and the yield was 938 g. The emulsion for 750 nm photosensitive layer had J-band type spectral sensitivity.

Compound used in chemical sensitization	Amount added
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene	0.39g
Triethyl thiourea	3.3mg
Nucleic acid decomposed material	0.39g
NaCl	0.15g
KI	0.12g
Anti-fogging agent (2)	0.10g
Preservative (1)	0.07g

Composition of dye solution	Amount added
Sensitizing dye (2)	0.19g
Methanol	18.7cc

Photosensitive silver halide emulsion (3) [emulsion for 1st layer (810 nm photosensitive layer)]

Solutions (I) and (II) each having the composition shown in Table 26 were added to an aqueous solution having the composition shown in Table 25 over a period of 18 minutes with sufficient stirring, and 10 minutes later, solutions (III) and (IV) each having the composition shown in Table 26 were added over a period of 24 minutes.

Composition
H₂O	620cc
Lime-processed gelatin	20g
KBr	0.3g
NaCl	2g
Solvent for silver halide (1)	0.03g
Sulfuric acid (1N)	16cc
Temperature	50°C

	(I) solution	(II) solution	(III) solution	(IV) solution
AgNO₃	30.0g	None	70.0g	None
KBr	None	13.7g	None	44.1g
NaCl	None	3.62g	None	2.4g
K₂IrCl₆	None	None	None	0.02mg
Total amount	Water is added up to 180ml	Water is added up to 181ml	Water is added up to 242ml	Water is added up to 250ml

The mixture was washed with water and desalted (conducted at a pH of 3.8 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 7.4 and pAg to 7.8 before chemical sensitization at 60°C. The compounds used in the chemical sensitization are shown in Table 27. The resulting emulsion was a monodispersion cubic silver chloride bromide emulsion having a variation coefficient of 9.7% and an average particle size of 0.32 µm, and the yield was 680 g.

Compound used in chemical sensitization	Amount added
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene	0.38g
Triethyl thiourea	3.1mg
Anti-fogging agent (2)	0.19g
Preservative (1)	0.07g
Preservative (2)	3.13g

Next, a method for preparing a gelatin dispersion of colloid silver is described.
A solution having the composition shown in Table 29 was added to an aqueous solution having the composition shown in Table 28 over a period of 24 minutes with sufficient stirring. Next, the mixture was washed with water using a flocculating agent a, then 43 g of lime-processed ossein gelatin was added to control pH to 6.3. The resulting product had an average particle size of 0.02 µm, and the yield was 512 g (dispersion containing 2% of silver and. 6.8% of gelatin).

Composition

H₂O 620cc

Dextrin 16g

NaOH (5N) 41cc

Temperature 30°C

composition

H₂O 135cc

AgNO₃ 17g
Next, a method for preparing a gelatin dispersion of a hydrophobic additive is described.
Gelatin dispersions of a yellow dye-forming coupler (1), a magenta dye-forming coupler (1), a cyan coupler dye-forming (1), and a developing agent were prepared respectively according to the formulations shown in Table 30. Namely, oil phase components were heated to about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed. It was then dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
A gelatin dispersion of an anti-fogging agent (4) was prepared according to the formulation shown in Table 31. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.
A gelatin dispersion of a reducing agent (1) was prepared according to the formulation shown in Table 32. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion. Further, ethyl acetate was removed from the resulting dispersion using a vacuum organic solvent removing apparatus.
A dispersion of a polymer latex (a) was prepared according to a formulation shown in Table 33. Namely, to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 33 was added an anionic surfactant (6) over a period of 10 minutes with stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using an ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth.

Dispersion composition

Polymer latex (a) aqueous solution (solid content: 13%) 108ml

Surfactant (5) 20g

Anionic surfactant (6) 600ml

Water 1232ml
A gelatin dispersion of a reducing agent (1) was prepared according to the formulation shown in Table 34. Namely, oil phase components were dissolved at room temperature, to this solution were added aqueous phase components heated to about 40°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a dispersion. Further, water added and the mixture was stirred to give a uniform dispersion.
A gelatin dispersion of zinc hydroxide was prepared according to the formulation shown in Table 35. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using a glass bead having an average particle size of 0.75 mm by a mill. Further, the glass bead was separated and removed, to give a uniform dispersion.

Dispersion composition

Zinc hydroxide 15.9g

Carboxymethylcellulose 0.7g

Sodium polyacrylate 0.07g

Lime-processed gelatin 4.2g

Water 100ml

Preservative (2) 0.4g
Next, a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed. Then, methylene chloride was removed by using a vacuum solvent removing apparatus to give a uniform dispersion having an average particle size of 4.3 µm.

The above-described products were used to produce the photosensitive elements 201 shown in Tables 36 and 37.

Composition of main materials of lightsensitive element 201
NO of layer	Name of layer	Additive	Amount added (mg/m²)
7th layer	Protective layer	Acid-processed gelatin	442
	Reducing agent (1)	47
	Solvent having a high boiling point (1)	30
	Colloid silver particle	2
	Matting agent (PMMA resin)	17
	Suriactant (1)	16
	Surfactant (2)	9
	Surfactant (3)	2
6th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Polymer latex (a) dispersion	5
	Water-soluble polymer (1)	4
	Calcium nitrate	6
5th layer	Red lightsensitive layer	Lime-processed gelatin	452
	Lightsensitive silver halide emulsion (1)	301
	Magenta dye forming coupler (1)	420
	Developing agent (2)	336
	Anti-fogging agent (2)	15
	Solvent having a high boiling point (2)	444
	Surfactant (1)	12
	Water-soluble polymer (1)	10
4th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Polymer latex (a) dispersion	5
	Water-soluble polymer (1)	4
	Calcium nitrate	6

Structure of main materials of lightsensitive element 201 (cont.)
NO of layer	Name of layer	Additive	Amount added Amount added (mg/m²)
3rd layer	Second infrared lightsensitive layer	Lime-processed gelatin	373
Lightsensitive silver halide emulsion (2)	106
Cyan dye forming coupler (1)	390
Developing agent (1)	312
Anti-fogging agent (2)	14
Solvent having a high boiling point	412
Surfactant (1)	11
Water-soluble polymer (1)	11
2nd layer	Intermediate layer	Lime-processed gelatin	862
Anti-fogging agent (4)	7
Solvent having a high boiling point (2)	101
Solvent having a high boiling point (5)	9
Surfactant (1)	21
Surfactant (4)	21
Water-soluble polymer (2)	25
Zinc hydroxide	750
Calcium nitrate	6
1st layer	First infrared lightsensitive layer	Lime-processed gelatin	587
Lightsensitive silver halide emulsion (3)	311
Yellow dye forming coupler (1)	410
Developing agent (3)	328
Anti-fogging agent (2)	15
Solvent having a high boiling point (4)	433
Surfactant (1)	12
Water-soluble polymer (2)	40
Hardener (1)	45
Substrate (substrate obtained by aluminum vapor deposition on a 20 µm PET and subsequent coating of gelatin on the back surface as an undercoat)

Hardener (1) CH₂ = CHSO₂CH₂SO₂ CH = CH₂

Organic solvent having a high boiling point (5)
C₂₆H_48.9Cl_7.1 (En-para 40 [manufactured by Ajinomono Co., Inc.]

Next, photosensitive elements 202 to 212 were prepared in the same manner as for the photosensitive element 201 except that the developing agents were changed to developing agents of yellow, magenta and cyan and the compounds used in the present invention as shown in Table 38.
Next, image output was conducted using the photosensitive elements 201 to 212 and image receiving element R101 under heating conditions of 83°C for 35 seconds or 78°C for 35 seconds, by a digital color printer FIJIX PICTOGRAPHY PG-3000 manufactured by Fuji Photo Film Co., Ltd. The resulting image was a clear color image. {Maximum density and minimum density were measured by using a reflection density meter X-lite 304 manufactured by X-lite Corp.}
The discrimination of the resulting image was evaluated by d-value in the same manner as in Example 1.

The results are shown in Table 39.

Lightsensitive element	d value (83 to 35 seconds)	d value (78 to 35 seconds)
201	Y M Cy	0.25 0.19 0.18	Y M Cy	0.38 0.28 0.29
202	Y M Cy	0.16 0.13 0.14	Y M Cy	0.18 0.15 0.15
203	Y M Cy	0.17 0.14 0.13	Y M Cy	0.19 0.16 0.15
204	Y M Cy	0.16 0.14 0.14	Y M Cy	0.19 0.15 0.16
205	Y M Cy	0.17 0,14 0.15	Y M Cy	0.18 0.15 0.16
206	Y M Cy	0.18 0.14 0.13	Y M Cy	0.19 0.15 0.15
207	Y M Cy	0.18 0.15 0.15	Y M Cy	0.20 0.17 0.18
208	Y M Cy	0.16 0.12 0.13	Y M Cy	0.19 0.14 0.14
209	Y M Cy	0.27 0.20 0.19	Y M Cy	0.39 0.28 0.28
210	Y M Cy	0.17 0.14 0.14	Y M Cy	0.20 0.15 0.16
211	Y M Cy	0.26 0.19 0.20	Y M Cy	0.38 0.28 0.29
212	Y M Cy	0.16 0.13 0.13	Y M Cy	0.18 0.15 0.15

It is understood that the photosensitive element in accordance with the present invention is not easily affected by differences in the processing conditions, and can provide an image having an excellent discrimination even under low temperature developing conditions. Each photosensitive element was left for 5 days under 45°C -80%RH, then image formation was conducted under conditions of 83°C for 35 seconds as described above. The photosensitive element in accordance with the present invention provided a clear color image.
As described above, the heat developing color photosensitive material in accordance the present invention can provide an excellent image in an extremely short developing time and is not easily affected by variations in processing conditions. Further, the heat developing color photosensitive material is able to provide an image in lower temperature processing conditions and has excellent ptorability.

Example 3

A method for preparing a photosensitive element (heat developing photosensitive material) is described below.
Firstly, a method for producing a photosensitive silver halide emulsion is described.

Photosensitive silver halide emulsion (1) [for red sensitive emulsion layer]

A solution (I) having the composition shown in Table 41 was added to an aqueous solution having the composition shown in Table 40 at a constant flow rate with sufficient stirring over a period of 9 minutes, and a solution (II) was added at a constant flow rate 10 seconds before the addition of the solution (I) over a period of 9 minutes and 10 seconds. 36 minutes after the addition, a solution (III) having the composition shown in Table 41 was added at a constant flow rate over a period of 24 minutes, and a solution (IV) was added at a constant flow rate simultaneously with the solution (III) over a period of 25 minutes.

The mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 880 g of lime-processed ossein gelatin was added to control pH to 6.0 before the addition of 12. 8 g of ribonucleic acid dissociated compound and 32 mg of trimethylthiourea, and the mixture was chemically sensitized for 71 minutes at 60°C, then, 2.6 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 3.2 g of a dye (a), 5.1 g of KBr and 2.6 g of a stabilizer (1) described below were added one by one, and the resulting mixture was cooled. In this manner, 28.1 kg of monodispersed cubic silver chloride bromide emulsion having an average particle size of 0.35 µm was obtained.

Photosensitive silver halide emulsion (2) [for green sensitive emulsion layer]

Solutions (I) and (II) each having the composition shown in Table 43 were simultaneously added to an aqueous solution having the composition shown in Table 42 at a constant flow rate with sufficient stirring over a period of 9 minutes. 5 minutes after the addition, solutions (III) and (IV) each having the compositions shown in Table 43 were simultaneously added at a constant flow rate over a period of 32 minutes. After completion of the addition of the solutions (III) and (IV), 60 ml of a methanol solution of dyes (containing 360 mg of a dye (b1) and 73.4 mg of a dye (b2)) was added in one time.

The mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.6 before the addition of 1.8 mg of sodium thiosulfate and 180 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and the mixture was chemically sensitized at 60°C, then 90 mg of an anti-fogging agent (1), and the resulting mixture was cooled. In this manner, 635 g of monodispersed cubic silver chloride bromide emulsion having an average particle size of 0.30 µm was obtained.

Photosensitive silver halide emulsion (3) [for blue sensitive emulsion layer]

Solutions (I) and (II) each having the compositions shown in Table 45 were added to an aqueous solution having the composition shown in Table 44 in a manner that the solution (II) was added first, and 10 seconds later, the solution (I) was added over a period of 30 minutes each with sufficient stirring. 2 minutes after completion of the addition of the (I) solution, a solution (V) was added, and 5 minutes after completion of the addition of the solution (II), a solution (IV) was added over a period of 28 minutes, and 10 seconds later, a solution (III) was added over a period of 27 minutes and 50 seconds.

The mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 1230 g of lime-processed ossein gelatin and 2.8 mg of a compound (b) were added to control pH to 6.1 and pAg to 8.4 before addition of 24.9 mg of sodium thiosulfate, and the mixture was chemically sensitized at 60°C, then, after 13.1 g of a dye (c) and 118 ml of a compound (c) were added successively, the resulting mixture was cooled. The halide particles in the resulted emulsion were potato-like particles, and had an average particle size of 0.53 µm, and the yield was 30700 g.

Next, a method for preparing a gelatin dispersion of a hydophobic additive is described.
Gelatin dispersions of a yellow dye-forming coupler, a magenta dye-forming coupler, a cyan dye-forming coupler, and a developing agent were prepared respectively according to formulations shown in Table 46. Namely, oil phase components were heated to about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
A gelatin dispersion of an anti-fogging agent (4) and reducing agent (1) was prepared according to the formulation shown in Table 47. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.

Organic solvent having a high boiling point (5)
(En-para 40 [manufactured by Ajinomono Co., Inc.]) C₂₆H_48.9Cl_7.1
A dispersion of a polymer latex (a) was prepared according to the formulation shown in Table 48. Namely, to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 48 was added an anionic surfactant (6) over a period of 10 minutes while stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using an ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth.

Dispersion composition

Polymer latex (a) aqueous solution (solid content: 13%) 108ml

Surfactant (5) 20g

Surfactant (6) 600ml

Water 1232ml
A gelatin dispersion of zinc hydroxide was prepared according to the formulation shown in Table 49. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using glass beads having an average particle size of 0.75 mm by a mill. Further, the glass beads were separated and removed, to give a uniform dispersion.

Dispersion composition

Zinc hydroxide 15.9g

Carboxymethylcellulose 0.7g

Sodium polyacrylate 0.07g

Lime-processed gelatin 4.2g

Water 100ml

Preservative (2) 0.4g
Next, a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed. Then, methylene chloride was removed by a vacuum solvent removing apparatus to give a uniform dispersion having an average particle size of 4.3 µm.

The above-described products were used to produce the photosensitive elements 301 shown in Tables 50 and 51.

Structure of main materials of heat developable photosensitive material 301
NO of layer	Name of layer	Additive	Amount added (mg/m²)
7th layer	Protective layer	Acid-processed gelatin	387
	Matting agent (PMMA resin)	17
	Surfactant (2)	6
	Surfactant (3)	20
	Polymer latex (a) Dispersion	10
6th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Reducing agent (1)	57
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Water-soluble polymer (1)	5
	Zinc hydroxide	558
	Calcium nitrate	6
5th layer	Blue lightsensitive layer	Lime-processed gelatin	587
	Lightsensitive silver halide emulsion (3)	399
	Yellow dye forming coupler (4)	410
	Developing agent D-1	328
	Anti-fogging agent (3)	15
	Solvent having a high boiling point (4)	433
	Surfactant (1)	12
	Water-soluble polymer (1)	40
4th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Reducing agent (1)	57
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Water-soluble polymer (1)	4
	Zinc hydroxide	341
	Calcium nitrate	8

Structure of main materials of heat developable photosensitive material 301 (cont.)
NO of layer	Name of layer	Additive	Amount added (mg/m²)
3rd layer	Green lightsensitive layer	Lime-processed gelatin	452
	Lightsensitive silver halide emulsion (2)	234
	Magenta dye forming coupler (8)	420
	Developing agent D-13	336
	Anti-fogging agent (2)	15
	Solvent having a high boiling point (4)	444
	Surfactant (1)	12
	Water-soluble polymer (1)	10
2nd layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Reducing agent (1)	57
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Water-soluble polymer (1)	10
	Calcium nitrate	6
1st layer	Red lightsensitive layer	Lime-processed gelatin	373
	Lightsensitive silver halide emulsion (1)	160
	Cyan dye forming coupler (19)	390
	Developing agent D-11	312
	Anti-fogging agent (2)	14
	Solvent having a high boiling point (4)	412
	Surfactant (1)	11
	Water-soluble polymer (2)	25
	Hardener (1)	45
	Preservative (3)	45
Substrate (substrate obtained by aluminum vapor deposition on a 20 µm PET and subsequent coating of gelatin on the back surface as an undercoat)

Hardener (1) CH₂=CHSO₂CH₂SO₂CH=CH₂

Next, heat developing photosensitive materials 302 to 321 were produced in the same manner as described above, except that the developing agent, coupler and the compounds used in the present invention represented by the general formulae (II) and (III) were added to the 1st, 3rd and 5th layers or 2nd, 4th and 6th layers in the amounts shown in Tables 52 and 53.
Next, image output was conducted using the above-described heat developing photosensitive elements 301 to 321 and image receiving element R101, as in Example 1 in heating conditions of 80°C for 30 seconds or 75°C for 30 seconds by PICTOSTAT 330 manufactured by Fuji Photo Film Co., Ltd. The image output on a dye fixing material was a clear color image. {Maximum density and minimum density were measured by using a reflection density meter X-lite 304 manufactured by X-lite Corp.}
The discrimination of the resulting image was evaluated by d-value = (Minimum density/Maximum density) (when d value is low, discrimination is excellent).
The results are shown in Tables 52 and 53. It is understood that the heat developing photosensitive material used in the present invention can provide an image having an excellent discrimination even under low temperature developing conditions.
Each heat developing photosensitive material was left for 5 days under 60°C -60%RH, then image formation was conducted in conditions of 80°C for 30 seconds as described above, and preservability of the heat developing photosensitive material was evaluated. The heat developing photosensitive material used in the present invention could provide a clear color image even after storage.

Example 4

Image receiving elements (dye fixing materials) were produced in the same manner as in Example 1.
Next, a method for producing a photosensitive element (heat developing photosensitive material) is described.
First, a method for producing a photosensitive silver halide emulsion is described.

Solutions (I) and (II) each having the compositions shown in Table 55 were simultaneously added to an aqueous solution having the composition shown in Table 54 with sufficient stirring over a period of 13 minutes, and 10 minutes later, solutions (III) and (IV) each having the compositions shown in Table 55 were added over a period of 33 minutes.

	(I) solution	(II) solution	(III) solution	(IV) solution
AgNO₃	30.0g	None	70.0g	None
KBr	None	13.7g	None	44.2g
NaCl	None	3.62g	None	2.4g
K₂IrCl₃	None	None	None	0.039mg
Total amount	Water is added up to 126ml	Water is added up to 132ml	Water is added up to 254ml	Water is added up to 252ml

13 minutes after initiation of the addition of the solution (III), 150 cc of an aqueous solution containing 0.350% of a sensitizing dye (1) was added over 27 minutes.
The mixture was washed with water and desalted (conducted at a pH of 4.1 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.9, and the mixture was chemically sensitized at 60°C. The compound used in the chemical sensitization is shown in Table 56.

The resulting emulsion (630 g) was a monodispersed cubic silver chloride bromide emulsion having a variation coefficient of 10.2%, and an average particle size of 0.20 µm.

Solutions (I) and (II) each having the compositions shown in Table 58 were simultaneously added to an aqueous solution having the composition shown in Table 57 with sufficient stirring over a period of 18 minutes. 10 minutes after the addition, solutions (III) and (IV) each having the compositions shown in Table 58 were added over a period of 24 minutes.

	(I) solution	(II) solution	(III) solution	(IV) solution
AgNO₃	30.0g	None	70.0g	None
KBr	None	13.7g	None	44.2g
NaCl	None	3.62g	None	2.4g
K₄[Fe(CN)₆]·H₂O	None	None	None	0.07g
K₂IrCl₆	None	None	None	0.04mg
Total amount	Water is added up to 188ml	Water is added up to 188ml	Water is added up to 250ml	Water is added up to 250ml

The mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 22 g of lime-processed ossein gelatin which had been subjected to de-calcium treatment (calcium content: 150 PPM or less) was added, and the mixture was dispersed at 40°C, and 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to control pH to 5.9 and pAg to 7.8. Then, the mixture was chemically sensitized at 70°C using chemicals shown in Table 59. Further, at the end of the chemical sensitization, sensitizing dye was added in the form of a methanol solution (solution having the composition shown in Table 60). Further, after chemical sensitization, the solution was cooled down to 40°C, to this was added 200 g of a gelatin dispersion of a stabilizer (1) described later, and they were sufficiently stirred before being stored. The resulting emulsion was a monodispersion cubic silver chloride iodide having a variation coefficient of 12.6% and an average particle size of 0.25 µm, and the yield was 938 g. The emulsion for 750 nm photosensitive layer had J-band type spectral sensitivity.

Drug used in chemical sensitization	Amount added
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene	0.39g
Triethyl thiourea	3.3mg
Nucleic acid decomposed material	0.39g
NaCl	0.15g
KI	0.12g
Anti-fogging agent (2)	0.10g
Preservative (1)	0.07g

Solutions (I) and (II) each having the composition shown in Table 62 were added to an aqueous solution having the composition shown in Table 61 over a period of 18 minutes with sufficient stirring, and 10 minutes later, solutions (III) and (IV) each having the compositions shown in Table 62 were added over a period of 24 minutes.

The mixture was washed with water and desalted (conducted at a pH of 3.8 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 7.4 and pAg to 7.8 before chemical sensitization at 60°C. The compounds used in the chemical sensitization are shown in Table 63. The resulting emulsion was a monodispersion cubic silver chloride bromide emulsion having a variation coefficient of 9.7% and an average particle size of 0.32 µm, and the yield was 680 g.

Drug used in chemical sensitization	Amount added
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene	0.38g
Triethyl thiourea	3.1mg
Anti-fogging agent (2)	0.19g
Preservative (1)	0.07g
Preservative (2)	3.13g

Next, a method for preparing a gelatin dispersion of colloid silver is described.
A solution having the composition shown in Table 65 was added to an aqueous solution having the composition shown in Table 64 over a period of 24 minutes with sufficient stirring. Next, the mixture was washed with water using a flocculating agent a, then 43 g of lime-processed ossein gelatin was added to control pH to 6.3. The resulted product had an average particle size of 0.02 µm, and the yield was 512 g (dispersion containing 2% of silver and 6.8% of gelatin).

Composition

H₂O 620cc

Dextrin 16g

NaOH(5N) 41cc

Temperature 30°C

Composition

H₂O 135cc

AgNO₃ 17g
Next, a method for preparing a gelatin dispersion of a hydrophobic additive is described.
Gelatin dispersions of a yellow coupler, a magenta coupler, a cyan coupler, and a developing agent were prepared respectively according to the formulations shown in Table 66. Namely, oil phase components were heated to about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
A gelatin dispersion of an anti-fogging agent (4) and a reducing agent (1) was prepared according to the formulation shown in Table 67. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.
A gelatin dispersion of a reducing agent (2) was prepared according to the formulation shown in Table 68. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was di000spersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion. Further, ethyl acetate was removed from the resulting dispersion using a vacuum organic solvent removing apparatus.
A dispersion of a polymer latex (a) was prepared according to the formulation shown in Table 69. Namely, an anionic surfactant (6) was added to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 31 over a period of 10 minutes while stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using a ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth.

Dispersion composition

Polymer latex (a) aqueous solution (solid content: 13%) 108ml

Surfactant (5) 20g

Surfactant (6) 600ml

Water 1232ml
A gelatin dispersion of a stabilizing agent (1) was prepared according to the formulation shown in Table 70. Namely, oil phase components were dissolved at room temperature, to this solution were added aqueous phase components heated to about 40°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a dispersion. Further, water added and the mixture was stirred to give a uniform dispersion.
A gelatin dispersion of zinc hydroxide was prepared according to a formulation shown in Table 71. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using glass beads having an average particle size of 0.75 mm by a mill. Further, the glass beads were separated and removed, to give a uniform dispersion.

Dispersion composition

Zinc hydroxide 15.9g

Carboxymethylcellulose 0.7g

Sodium polyacrylate 0.07g

Lime-processed gelatin 4.2g

Water 100ml

Preservative (2) 0.4g
Next, a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed. Then, methylene chloride was removed by a vacuum solvent removing apparatus to give a uniform dispersion having an average particle sized of 4.3 µm.

Hardener (1) CH₂=CHSO₂CH₂SO₂CH=CH₂
Organic solvent having a high boiling point (5)
(En-para 40 [manufactured by Ajinomono Co., Inc.]) C₂₆H_48.9Cl_7.1

The above-described products were used to produce photosensitive elements 401 shown in Tables 72 and 73.

Composition of main materials of heat developable photosensitive material 401
NO of layer	Name of layer	Additive	Amount added (mg/m²)
7th layer	Protective layer	Acid-processed gelatin	442
	Reducing agent (2)	47
	Solvent having a high boiling point (1)	30
	Colloid silver particle	2
	Matting agent (PMMA resin)	17
	Surfactant (1)	16
	Surfactant (2)	9
	Surfactant (3)	2
6th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Reducing agent (1)	57
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Polymer latex (a) dispersion	5
	Water-soluble polymer (1)	4
	Calcium nitrate	6
5th layer	Red lightsensitive layer	Lime-processed gelatin	452
	Lightsensitive silver halide emulsion (1)	301
	Magenta dye forming coupler (9)	420
	Developing agent D-9	336
	Anti-fogging agent (2)	15
	Solvent having a high boiling point (2)	444
	Surfactant (1)	12
	Water-soluble polymer (1)	10
4th layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Reducing agent (1)	57
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Polymer latex (a) dispersion	5
	Water-soluble polymer (1)	4
	Calcium nitrate	6

Composition of main materials of heat developable photosensitive material 401 (cont.)
NO of layer	Name of layer	Additive	Amount added (mg/m²)
3rd layer	Second infrared lightsensitive layer	Lime-processed gelatin	373
	Lightsensitive silver halide emulsion (2)	106
	Cyan dye forming coupler (20)	390
	Developing agent D-7	312
	Anti-fogging agent (2)	14
	Solvent having a high boiling point (5)	412
	Surfactant (1)	11
	Water-soluble polymer (1)	11
2nd layer	Intermediate layer	Lime-processed gelatin	862
	Anti-fogging agent (4)	7
	Reducing agent (1)	57
	Solvent having a high boiling point (2)	101
	Solvent having a high boiling point (5)	9
	Surfactant (1)	21
	Surfactant (4)	21
	Water-soluble polymer (2)	25
	Zinc hydroxide	750
	Calcium nitrate	6
1st layer	First infrared lightsensitive layer	Lime-processed gelatin	587
	Lightsensitive silver halide emulsion (3)	311
	Yellow dye forming coupler (4)	410
	Developing agent D-2	328
	Anti-fogging agent (2)	15
	Solvent having a high boiling point (4)	433
	Surfactant (1)	12
	Water-soluble polymer (2)	40
	Hardener (1)	45
Substrate (substrate obtained by aluminum vapor deposition on a 20 µm PET and subsequent coating of gelatin on the back surface as an undercoat)

Next, heat developing photosensitive materials 402 to 412 were prepared in the same manner as for the heat developing photosensitive material 401, except that the developing agents were changed to developing agents of yellow, magenta and cyan and the compounds used in the present invention as shown in Tables 74 and 75.
Next, image output was conducted using the heat developing photosensitive materials 201 to 212 and image receiving elements under heating conditions of 83°C for 35 seconds or 78°C for 35 seconds by a digital color printer FIJIX PICTOGRAPHY PG-3000 manufactured by Fuji Photo Film Co., Ltd. The output image was a clear color image. {Maximum density and minimum density were measured by using a reflection density meter X-lite 304 manufactured by X-lite Corp.}
The discrimination of the resulting image was evaluated by d-value in the same manner as in Example 3.
The results are shown in Tables 74 and 75.
It is understood that the heat developing photosensitive material used in the present invention can provide an excellent image even under low temperature developing conditions. Each heat developing photosensitive material was left for 5 days under 45°C -80%RH, then image formation was conducted under conditions of 83°C for 35 seconds as described above. The heat developing photosensitive material used in the present invention provided a clear color image.
The heat developing color photosensitive material used in the present invention can provide an excellent image in a short developing time and is not easily affected by variations in processing conditions. Further, the heat developing color photosensitive material is able to provide an image under lower temperature processing conditions.

Claims

A color image forming method, wherein a color image which is formed by a diffusive dye is diffusion-transferred onto a dye fixing material by heat developing a heat developing color photosensitive material superimposed on the dye fixing material in the presence of a small amount of water and a base, wherein said heat developing color photosensitive material comprises a substrate carrying thereon a photosensitive silver halide, a binder, a compound represented by the general formula (I) or (D) and a compound which forms or releases the diffusive dye by reaction with an oxidized product of the compound represented by the general formula (I) or (D), further comprising at least one of the compounds represented by the general formulae (II-a), (II-b), (IV-a), (IV-b), (IV-c), (IV-d), (IV-e), (IV-f) and (IV-g);

wherein, Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group, and both Q¹ and C represent an atomic group forming an unsaturated ring:

wherein, R₁ to R₄ each independently represents a hydrogen atom or substituent thereof, A represents a hydroxyl group or substituted amino group. X represents a linkage group with a valency of two or more selected from the group consisting of -NHCO-, -NHSO-, -NHSO₂-, and -NHPO<; Y represents a bivalent linkage group, Z represents a nucleophilic group which can attack the X group when the compound represented by the formula D is oxidized, R₁ and R₂ and, R₃ and R₄ each independently may bond with each other to form a ring;

wherein, Ball represents an organic ballasting group which allows the compounds represented by the formulae to become non-diffusive, when R¹ is non-diffusive, Ball may not be required;

Y¹ represents a carbon atom group required for completing a benzene nucleus or naphthalene nucleus;

R¹ represents an alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heretocyclic group;

R² represents a hydrogen atom, halogen atom, alkyl group. cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acylamino group, alkylthio group, or arylthio group;

n represents an integer from 0 co 5, and when n is 2 to 5, R² may be the same or different, or a plurality may bond together to form a ring;

when Y¹ represents an atomic group required for completing a naphthalene nucleus, Ball and R² can be bonded co any one of the rings formed:
HOOC-R²³
R²⁵-NHSO₂R²⁶ R²⁷-CONHCO-R²⁸
HO-R²⁹

wherein, A represents a bivalent electron attractive group, R²¹ represents an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylamino group, an anilino group or a haterocyclic group; 1 represents an integer of 1 or 2; R²² represents an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom, m represents an integer from 0 to 4; Q² represents a benzene ring or heterocyclic ring which may be condensed with a phenol ring;

R₂₃ represents an alkyl group, an aryl group or a heterocyclic group;

Y² represents an aryl group, an alkyl group, a heterocyclic group, a -P(=O) (Rb) -Ra group, or a -C(=O)-Ra group; R^'24 represents an alkylene group, an arylene group or an aralkylene group; R²⁴ represents an alkyl group or an aryl group; wherein, Y² and R²⁴ can not represent an alkyl group simultaneously; Ra and Rb each independently represent an alkyl group, an aryl group, an amino group, an alkoxy group, or an aryloxy group;

n represents an integer from 1 to 5;

R²⁵ represents a hydrogen atom, an alkyl group, an aryl group, a phenylsulfonyl group, or an acyl group; R²⁶ and R²⁴ have the same meaning; R²⁵ and R²⁶ may close a ring co form a 5- co 7-membered ring;

R²⁷ and R²⁸ have the same meaning as R²⁴, and may close ring to form a 5- to 7-membered ring; and R²⁹ represents an alkyl group having 12 to 50 carbon atoms in total;
represents a 5 to 7-membered heterocyclic ring;
with the proviso that the compound
is excluded as a compound of formula (D).
The method according to claim 1, wherein the heat developing color photosensitive material comprises a substrate carrying thereon a photosensitive silver halide, a binder, a compound represented by the general formula (D) and a compound which forms or releases a diffusive dye by reaction with an oxidized product of the compound represented by the general formula (D), further comprising at least one of compounds represented by the general formulae (II-a)or (II-b),