JP2001005133A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material excellent in dye formation efficiency by incorporating a specified color developing agent. SOLUTION: The silver halide color photographic sensitive material contains a color developing agent of the formula, wherein A is a group selected from among -OH, -OR11, -NH2,-NHR12 and-NR13R14, R11 and R14 are each an alkyl or substituted aryl, R12 and R13 are each a substituent, R1-R4 are each H or a substituent, the sum of the Hammett's substituent constants σp of the substituents R1-R4 is <0 and the sum of the Hannmett's substituent constants σm is >=0, Ar is an optionally substituted aromatic group, substituents of the aromatic group may bond to each other to form a ring, Ar may be an aromatic group having substituents in the o-positions such as o-substituted phenyl and at least one of the substituents R1-R3 has >=8 ballast groups or the total number of carbon atoms in the substituents of the aromatic group Ar is >=8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a "light-sensitive material") and an image forming method, and more particularly, to a silver halide color photographic material excellent in image discrimination. The present invention relates to a photosensitive material and an image forming method, particularly to a heat-developable color photographic image forming method.

[0002]

2. Description of the Related Art A photographic method using silver halide has been used most widely since it has superior photographic characteristics such as sensitivity and gradation control as compared with other photographic methods such as electrophotography and diazo photography. I have been.

[0003] In recent years, image forming processing methods for photosensitive materials using silver halide have been simplified from conventional wet processing to instant photographic systems incorporating a developing solution, and dry thermal development processing by heating or the like. Systems have been developed that can rapidly obtain images. The content of the photothermographic material is described in “Basics of Photographic Engineering (Non-Silver Photography) Corona Co., Tokyo, 1982, P242” and later, but the content is black and white, as represented by dry silver. Only the image forming method. Recently, as photothermographic color light-sensitive materials, products such as Pictrography and Pictrostat have been sold by Fuji Photo Film Co., Ltd. In the above-described simple and rapid processing method, a color image is formed using a redox coloring material to which a preformed die is connected. The most common method for forming a color image of a photographic light-sensitive material is a method utilizing a coupling reaction between a coupler and an oxidized developing agent. A heat-developable color light-sensitive material employing this method is also disclosed in U.S. Pat. Many ideas have been filed, such as U.S. Pat. Nos. 761,270, 4,021,240, JP-A-59-231539, and JP-A-60-128438. Each of the above photothermographic materials is characterized in that it contains a reducing developing agent.

The above-mentioned coupling type heat-developable color light-sensitive material was examined.
No. 40, JP-A-60-128438 and the like, p-sulfonamidophenol has been found to be a compound excellent in discrimination and raw preservability when incorporated in a light-sensitive material.

[0005] Further, the coupling method is advantageous in terms of sensitivity because the coupler does not absorb in the visible region before processing, compared to a system using a coloring material in which a preformed die is connected. Was. From this perspective,
The potential of p-sulfonamidophenol as a developing agent has been investigated by synthesizing various compounds.

As a result, although p-sulfonamidophenol is a compound which is excellent in raw preservability and gives a color image which is excellent in discrimination, it has been revealed as a problem that the dye-forming efficiency is low.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material and an image forming method, particularly a heat-developable color photographic image forming method, having excellent dye formation efficiency.

[0008]

The object of the present invention has been attained by the following constitutions.

1. A silver halide color photographic material comprising a color developing agent represented by the following general formula [1].

[0010]

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In the formula, A represents —OH, —OR ₁₁ , —NH ₂ ,
It represents a group selected from -NHR ₁₂ or -NR ₁₃ R _14, R
₁₁ and R ₁₄ represents an alkyl group, a substituted aryl group, R ₁₂
And R ₁₃ represent a substituent. R _{1 to} R ₄ represent a hydrogen atom or a substituent, and represent a group having a total Hammett substituent constant σp value of less than 0 and a total σm value of 0 or more. Ar
Represents a substituted or unsubstituted aromatic group. The substituents of the aromatic group may be bonded to each other to form a ring.

2. 2. The silver halide color photographic light-sensitive material as described in 1 above, wherein Ar in the general formula [1] is an aromatic group having a substituent at the ortho position.

3. 3. The silver halide color photographic material as described in 1 or 2, wherein Ar in the general formula [1] is an ortho-substituted phenyl group.

4. In the general formula [1], any one of the substituents of R _{1 to} R ₃ has a ballast group of 8 or more, or the total number of carbon atoms of the substituent of Ar is 8 or more. 4. The silver halide color photographic light-sensitive material according to any one of items 1 to 3.

[0015] 5. 5. The silver halide color photographic light-sensitive material as described in any one of the above items 1 to 4, wherein the support contains at least a photosensitive silver halide, a binder and a coupler.

6. 6. An image forming method, comprising thermally developing the silver halide color photographic light-sensitive material according to any one of the above items 1 to 5 at 60 ° C to 120 ° C.

That is, as a result of examining the dye formation efficiency in the developing section when p-sulfonamidophenol is used as a color developing agent, the effect is not clear,
The total substituent of the sulfonamide phenol is less than 0 as the sum of Hammett substituent constant σp values, and the sum of the σm values is 0.
Compounds having the above have been found to be very highly active. Furthermore, the inventor has searched for more preferred compounds, and that the ortho-position substituent of the sulfonyl group is bulky,
And that the leaving group has an electron donating ballast group,
It was found that this is an important factor for improving the dye formation efficiency.

Hereinafter, the present invention will be described in detail.

First, the compound represented by formula (1) will be described in detail. The compound represented by the general formula [1] is
It represents a developing agent (color developing agent) called p-sulfonamidophenol.

In the general formula [1], R _{1 to} R ₄ represent a hydrogen atom or a substituent, and a group having a total Hammett substituent constant σp value of less than 0 and a total σm value of 0 or more. Represent. As the substituent for R _{1 to} R ₄ , a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, Alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group,
Arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Preferred are an alkylcarbonyl group, an arylcarbonyl group and an acyloxy group.

The Hammett's rule for Hammett's substituent constant was described in 1935 in 1935 to discuss quantitatively the effect of substituents on the reaction or equilibrium of benzene derivatives. P. Hamme
This is an empirical rule proposed by tt, which is widely accepted today.

The substituent constants determined by the Hammett's rule include a σp value and a σm value. These values are described in many general documents. A. Edited by Dean, "Lange's Handbook of Chemist"
ry "12th edition, 1979 (McGraw-Hil
l) and “Chemical Area Special Issue” No. 122, pp. 96-103,
1979 (Nankodo), Chemical Review
w, Vol. 91, pp. 165-195, 1991.

In the present invention, the meaning is not limited to only those substituents having the values described in these documents.
Even if the value is unknown in the literature, it is naturally included as long as the value falls within the range when measured based on the Hammett's rule. 23, 0.39), chlorine atom (0.23, 0.
37), a cyano group (0.66, 0.56), a nitro group (0.78, 0.71), a trifluoromethyl group (0.
54, 0.43), tribromomethyl group (0.29,
0.28), trichloromethyl group (0.33, 0.3
2), carboxyl group (0.45, 0.37), acetyl group (0.50, 0.38), benzoyl group (0.4
3,0.34), an acetyloxy group (0.31, 0.3
9), trifluoromethanesulfonyl group (0.92,
0.79), methanesulfonyl group (0.72, 0.6
0), a benzenesulfonyl group (0.70, 0.61),
Methanesulfinyl group (0.49, 0.52), carbamoyl group (0.36, 0.28), methylcarbamoyl group (0.36, 0.35), methoxycarbonyl group (0.45, 0.37) , An ethoxycarbonyl group (0.
45, 0.37), a phenoxycarbonyl group (0.4
4,0.37), a pyrrolyl group (0.37, 0.47),
Methanesulfonyloxy group (0.36, 0.39), dimethoxyphosphoryl group (0.60, 0.42), sulfamoyl group (0.57, 0.46), phenyl group (-
0.01, 0.06), 4-methylphenyl group (−0.0.
03, 0.06), ethylene group (−0.04, 0.0
6), 3-thienyl group (-0.02, 0.03), benzoylamine group (-0.19, 0.02), methoxy group (-0.27, 0.12), ethoxy group (-0 .24,
0.10), methyl group (-0.17, -0.07), amino group (-0.66, -0.16), ureido group (-
0.24, -0.03), methanesulfonamide group (0.03, 0.20), acetylamino group (0.0
0, 0.21) and the like.

R ₄ is preferably a hydrogen atom, and R _{1 to} R
Preferred ₃ substituents represent groups having a total Hammett substituent constant σp value of less than 0 and a total σm value of 0 or more.

In the general formula [1], Ar represents a substituted or unsubstituted aromatic group. The substituents of the aromatic group may be bonded to each other to form a ring.

Examples of the substituent of the aromatic group include a hydrogen atom, a halogen atom, an amino group, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, Aryloxy group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group,
Arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Alkylcarbonyl group, arylcarbonyl group, acyloxy group, heterocyclic group, alkoxycarbonylamino group,
Represents an aryloxycarbonylamino group, a ureido group, a phosphorylamino group, or a carbamoyloxy group. R ₁ and R ₂ , and R ₃ and R ₄ may combine with each other to form a ring (for example, a naphthalene ring, a tetralin ring, a coumarin ring).

Particularly, the substituent at the ortho position is preferably a substituent other than a hydrogen atom.

It is preferable that the sum of Hammett constant σ values of the substituents of the aromatic group be 0 or less. As the Hammett constant σ value at the ortho position, the σp value is substituted. That is, the σp value is used in the ortho position, the σm value is used in the meta position, and the σp value is used in the para position.
The following is preferred.

In the present invention, among the substituents mentioned above,
Ortho substituent is a halogen atom, an amino group, an alkyl group, an aryl group, an acylamino group, a sulfonamide group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, phosphorylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group or carbamoyl group, preferably an alkyl group, aryl Groups, acylamino groups and sulfonamide groups are more preferred, and alkyl groups are particularly preferred.

In the general formula [1], R ₁₁ and R ₁₄ represent an alkyl group or a substituted aryl group, preferably a methyl group or an ethyl group.

In the general formula (1), R ₁₂ and R ₁₃ represent a substituent, and specifically, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylcarbonamide group, an arylcarbonamide group, Sulfonamide group, arylsulfonamide group, alkylthio group,
Arylthio, alkylcarbamoyl, arylcarbamoyl, alkylsulfamoyl, arylsulfamoyl, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyl, arylcarbonyl, acyloxy Are preferred.

The compound represented by the general formula [1] is preferably an oil-soluble compound for use for the purpose of the present invention. For this reason, it is necessary that at least one group having ballast property is contained. The ballast group referred to herein indicates an oil-solubilizing group, and is a group containing an oil-soluble partial structure having usually 8 to 80 carbon atoms, preferably 8 to 40 carbon atoms, and more preferably 10 to 40 carbon atoms. Therefore, it is preferable that R _{1 to} R ₄ , preferably R _{1 to} R ₃ , have a ballast group having 8 or more carbon atoms, or the total number of carbon atoms of the substituent of Ar is 8 or more. . The number of carbon atoms is more preferably 8
~ 80, more preferably 8 ~ 20.

As a method of adding the developing agent represented by the general formula [1], first, a coupler, a developing agent and a high-boiling organic solvent (for example, alkyl phosphate, alkyl phthalate, etc.) are mixed to obtain a mixture having a low boiling point. It can be dissolved in an organic solvent (eg, ethyl acetate, methyl ethyl ketone, etc.), dispersed in water using an emulsification dispersion method known in the art, and then added. Further, addition by the solid dispersion method described in JP-A-63-271339 is also possible. As described above, the color developing agent represented by the general formula [1] is used in a form incorporated in a photosensitive material, and is particularly preferably used as a photothermographic material. It is also useful as a photosensitive material.

The addition amount of the color developing agent represented by the general formula [1] has a wide range, but is preferably 0.01 to 100 times by mole, more preferably 0.1 to 1 times the coupler.
0 mole times is suitable, and the photosensitive material is preferably 0.01 to 1 times.
000 mmol / m ² , preferably 0.1 to 50 mmol
1 / m ² is more preferred.

<Synthesis of Developing Agent D-1> Developing agent D-1 was synthesized by the following synthesis route.

[0036]

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Acetonitrile (800 ml) and 3-methoxy-4-aminophenol (167 g, 1.2 mol) are kept at 0 ° C. or lower while stirring on a methanol-ice bath. Here, 81 ml (1 mol) of pyridine is added while passing a nitrogen stream. In a state where the solution is uniform and the temperature is kept at 5 ° C. or lower, 303 g (1 mol) of 2,4,6-triisopropylbenzenesulfonyl chloride is slowly dropped at a temperature in the flask of 10 ° C. or lower. After completion of the addition, the reaction is further stirred for 1 hour and then stirred for 1 hour at room temperature. The reaction mixture is poured into 10 liters of a 0.1N aqueous hydrochloric acid solution, and the precipitated crystals are separated by filtration. The crude crystals were recrystallized from 2 liters of methanol to obtain 404 g of crystals of the developing agent D-1 (83% yield).

Hereinafter, specific examples of the compound represented by the general formula [1] are shown, but the compound of the present invention is not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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In the present invention, a compound (coupler) that forms a dye by an oxidative coupling reaction is used as the dye-donating compound. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler, but a 4-equivalent coupler is preferred in the present invention.

First, in the present invention, the amino group which is the coupling site of the compound of the present invention is protected by a substituent, and the coupling site on the coupler side has a substituent during the coupling. This is because the reaction is inhibited by steric hindrance. Secondly, since this substituent is released as an anion after coupling, the leaving group on the coupler side must be released as a cation,
This is because such a leaving group cannot be formed with a normal 2-equivalent coupler.

Specific examples of the coupler include a four-equivalent and a two-equivalent, both of which are based on Theory of the Photographic Process (4th Ed Ed TH James, edited by Mac).
millan, 1977) pp. 291-334, and 3
54-361, JP-A-58-12353, 58
No. 149046, No. 58-149047, No. 59-
Nos. 11114, 59-124399, 59-17
No. 4835, No. 59-231439, No. 59-231
No. 540, No. 60-2951, No. 60-14242
And Nos. 60-23474 and 60-66249.

The couplers preferably used in the present invention are compounds generally called open-chain active methylene compounds, pyrazolone compounds, pyrazoloazole compounds, phenol compounds, naphthol compounds and pyrrolotriazole compounds, respectively. Is a compound of

The amount of the coupler to be added depends on its molar extinction coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, the ε of the dye formed by the coupling is 5,000 to 5,000. In the case of a coupler of about 500,000, the coating amount is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , more preferably about 0.05 to 5 mmol / m ^2. It is.

The light-sensitive material of the present invention basically comprises a support having a light-sensitive silver halide, a coupler as a dye-providing compound, a compound of the present invention, and a binder.
Further, if necessary, an organic metal salt oxidizing agent and the like can be contained. These components are often added to the same layer, but can be added to another layer as long as they can react.

To obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. . For example, there are three layers of a blue sensitive layer, a green sensitive layer, and a red sensitive layer, and a combination of a green sensitive layer, a red sensitive layer, and an infrared sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

The photosensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to improve color separation.

Generally, a base is required for processing a photographic light-sensitive material. In the light-sensitive material of the present invention, various base supply methods can be adopted. For example, when a base generating function is imparted to the light-sensitive material side, it can be introduced into the light-sensitive material as a base precursor. Such base precursors include, for example, salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution, Lossen rearrangement or Beckmann rearrangement. For this example, see U.S. Pat. No. 4,514,493.
No. 4,657,848 and the like.

In the case of using an embodiment in which a photosensitive material and a processing sheet are superposed and processed, a method of introducing a base or a base precursor into the processing sheet can also be used. As the base in this case, an organic base such as an amine derivative can be used in addition to the inorganic base.

Further, a reaction in which a base precursor is contained in each of the light-sensitive material side and the processing sheet side to generate a base by a reaction between the two can be used. Examples of such a two-agent reaction type base generation method include, for example, a method based on a reaction between a sparingly soluble basic metal salt and a chelating agent, and a method based on a reaction between a nucleophilic agent and an epoxy compound. This example is described in JP-A-63-198050 and the like.

The silver halide emulsion used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging.

A so-called core-shell emulsion having different phases in the grain interior and the grain surface layer may be used, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and is disclosed in JP-A-1-167743 and JP-A-4-22.
As described in No. 3463, a method of adjusting the gradation by mixing monodispersed emulsions is preferably used. Particle size is 0.1
To 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other.

Specifically, US Pat. No. 4,500,62
No. 6, column 50, 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17
029 (1978); 17643 (1978)
No. 22-22, p. 18716 (197
November 1989) p. 648, ibid. 307105 (198
Nov. 9) pages 863 to 865, JP-A-62-2531.
No. 59, No. 64-13546, JP-A-2-23654
No. 6, No. 3-110555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte, Inc. (P. Glafk)
ides, ChemieetPhisiquePhot
ographique, PaulMontel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographi).
cEmulsionChemistry, FocalP
ress, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zeli).
kmanetal. , MakingandCoatin
gPhotographicEmulsion, Foc
alPress, 1964) and the like, any of which can be used.

In the process of preparing the photosensitive silver halide emulsion used in the present invention, it is preferable to carry out so-called desalting for removing excess salts. As a means for this, a Nudel washing method performed by gelatinizing gelatin may be used,
In addition, inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, sodium polystyrene sulfonate), or gelatin derivatives (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic A sedimentation method using carbamoylated gelatin) may be used. The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly contained in the particles, or may be localized inside or on the surface of the particles. Specifically, JP-A-2-236542, JP-A-1-116637, and JP-A-5-116637.
Emulsions described in 181246 and the like are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion, a rhodan salt, ammonia, a tetra-substituted thioether compound or a silver halide solvent may be used as a silver halide solvent.
Organic thioether derivative described in No. 6
For example, a sulfur-containing compound described in No. 144319 can be used.

For other conditions, see the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte Co. (PG
lafkides, ChemieetPhisique
Photographique, PaulMonte
1, 1967), by Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Photog).
graphicEmulsionChemistry, F
ocalPress, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al.
L. Zelikmanetal. , Makingand
CoatingPhotographicEmulsi
on, FocalPress, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-5-142329).
No. 5-158124, U.S. Pat. No. 3,650,757). Further, the method of stirring the reaction solution may be any known stirring method.

The temperature and pH of the reaction solution during the formation of silver halide grains may be set as desired depending on the purpose.
The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. Chemical sensitization of a photosensitive silver halide emulsion includes known sulfur sensitization methods, selenium sensitization methods, and chalcogen sensitization methods such as tellurium sensitization methods, and gold, platinum, palladium, and the like for emulsions for conventional photosensitive materials. The noble metal sensitization method and reduction sensitization method used can be used alone or in combination (for example, JP-A-3-110555 and JP-A-5-110555).
241267). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. Sho 62-62).
253159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, the methods described in JP-A-5-45833 and JP-A-62-40446 can be used. The pH during chemical sensitization is preferably from 5.3 to 10.5, more preferably from 5.5 to 8.5, and the pAg is preferably from 6.0 to 10.5, more preferably from 6.8 to 9 0.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is 1 mg / silver equivalent.
The range is from m ^{2 to} 10 g / m ² .

In order to impart green-, red-, and infrared-sensitive color sensitivity to the photosensitive silver halide preferably used in the present invention, the photosensitive silver halide emulsion is spectrally enhanced with methine dyes and other dyes. I feel. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
Specific examples thereof include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828, and 5-45834. Can be These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,6
41, JP-A-63-23145).

The time when these sensitizing dyes are added to the emulsion may be at or before or after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,566. It may be before or after formation. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The amount of addition is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The additives used in such a step and the known photographic additives which can be used in the photothermographic material and the dye fixing material of the present invention are described in RDNo. No. 17643, ibid. No. 18716 and the same No. 307105, and the corresponding portions are summarized in the following table.

Type of Additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868, super sensitizer ~ page 649, right column 4. Optical brightener page 24 page 648 right column page 868 5. Antifoggant page 24-25 page 649 right column page 868-870 stabilizer 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, 頁 650, left column, ultraviolet absorbers. 7. Dye image stabilizer page 25 650 page left column page 872 8. Hardening agent page 26 page 651 left column 874-875 Binder page 26 page 651 left column pages 873 to 874 10. Plasticizer, lubricant page 27 page 650 right column page 876 11. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 12. Static, page 27, page 650, right column, pages 876 to 877 Inhibitor A hydrophilic binder is preferably used as a binder for the constituent layers of the photothermographic material. Examples thereof include those described in the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also,
U.S. Pat. No. 4,960,681, JP-A-62-245
No. 260 etc., ie, -CO
OM or -SO ₃ M (M is a hydrogen atom or an alkali metal) copolymer of homopolymer or a vinyl monomer each other or with other vinyl monomers, vinyl monomers having a (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Sumikagel L-5 manufactured by Chemical Co., Ltd.
H) is also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in 00,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above-mentioned organic silver salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

When the light-sensitive material of the present invention is used for a heat-developable light-sensitive material, a compound which activates development and stabilizes an image at the same time can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52. Also, JP-A-8-6
Compounds capable of fixing silver halide, such as those described in JP-A No. 9097, can also be used.

Examples of the hardening agent used for the constituent layers of the photothermographic material include Research Disclosure, US Pat. No. 4,678,739, column 41, and 4,791,04.
No. 2, JP-A-59-116655 and JP-A-62-2452.
No. 61, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc., N
-Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of gelatin applied. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material, or may be added in two or more layers.

In the constituent layers of the photothermographic material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples include the aforementioned Research Disclosure, US Pat. No. 5,089,
No. 378, No. 4,500,627, No. 4,614,7
02, JP-A-64-13546, pages (7) to (9),
(57)-(71) and (81)-(97), U.S. Pat. Nos. 4,775,610 and 4,626,500.
No. 4,983,494, JP-A-62-17474.
No. 7, No. 62-239148, No. 63-264747
No., JP-A-1-150135 and 2-110557
No. 2-178650, RD17643 (1978
Years) (24) to (25) and the like. These compounds are used in an amount of 5 × 10 ^-6 to 1 / mol silver.
× 10 ^-1 mol is preferable, and 1 × 10 ^-5 to 1 × 10
^-2 mol is preferably used.

In the constituent layers of the photothermographic material, a coating aid,
Various surfactants can be used for the purpose of improving releasability, improving slipperiness, preventing static charge, accelerating development, and the like. Specific examples of the surfactant are described in the aforementioned Research Disclosure, JP-A Nos. 62-173463 and 62-183457.

The constituent layers of the photothermographic material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-51-9053.
No. -20944, No. 62-135825 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin Is mentioned.

A matting agent can be used in the photothermographic material for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Matting agents such as silicon dioxide, polyolefin or polymethacrylate are disclosed in JP-A-61-8825.
JP-A-63-274944 and JP-A-63-27, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page 6 (29).
No. 4952. Other research
The compounds described in the disclosure can be used.

These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, the constituent layers of the photothermographic material include a thermal solvent, an antifoaming agent,
A germicidal and antibacterial agent, colloidal silica, and the like may be included.
Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3-11338, and JP-B-2-51496.

An image formation accelerator can be used in the photothermographic material. The image formation accelerator has a function of accelerating a redox reaction between a silver salt oxidizing agent and a reducing agent, accelerating a dye formation reaction, and the like. From a physicochemical function, a base or a base precursor, a nucleophilic compound, Boiling point organic solvent (oil),
It is classified into thermal solvents, surfactants, compounds that interact with silver or silver ions, and the like. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Various development stoppers can be used in the photothermographic material for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. More specifically, JP-A-62-253159 (31) to (32)
Page.

As a method of exposing and recording an image on the photothermographic material, for example, a method of directly photographing a landscape or a person using a camera or the like, or a method of exposing through a reversal film or a negative film using a printer or a enlarger. Method, a method of scanning and exposing the original image through slits and the like using a copier exposure device, etc., and scanning exposure by emitting light from light emitting diodes and various lasers (laser diodes, gas lasers, etc.) to image information via electric signals. (Japanese Unexamined Patent Publication (Kokai) No. 2-129625 and 5-176144)
, The methods described in JP-A-5-199372, JP-A-6-127022, etc.), CRT, liquid crystal display,
There is a method of outputting an image to an image display device such as an electroluminescence display or a plasma display and exposing the image directly or via an optical system.

As the light source for recording an image on the photothermographic material, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., as described above, US Pat. No. 4,500,626, column 56, Kaihei 2-533
No. 78 and 2-54672 can be used.

Further, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (KD)
P), lithium iodate, BaB ₂ O _{4, and} other inorganic compounds, urea derivatives, nitroaniline derivatives such as 3-methyl-4-nitropyridine-N-oxide (P
Nitropyridine-N-oxide derivatives such as OM)
The compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal produced using a computer represented by a signal, CG, or CAD can be used.

The photothermographic material may have a form having a conductive heating element layer as a heating means for heat development. The heat generating element in this case is described in JP-A-61-14554.
No. 4, etc. can be used. The heating temperature in the thermal development step is from 60C to 120C, and the heating time is from 0.1 second to 60 seconds.

As a heating method in the developing step, a heated block or plate is brought into contact with a heated plate, a hot presser, a heated roller, a heated drum, a halogen lamp heater, an infrared and far infrared lamp heater, or the like. Or passing through a high-temperature atmosphere. A method of superposing a photothermographic material and a dye fixing material is described in JP-A-62-253159 and JP-A-61-1472.
The method described on page 44 (27) can be applied.

As the support for the light-sensitive material of the present invention, those known in the art, in particular, as the support for the photothermographic material can be used. Examples of such a support include a paper support laminated with polyethylene, a polyester support represented by polyethylene terephthalate and polyethylene naphthalate, and the like. An example of such a support is disclosed in JP-A-63-18986.
No. 0 has a detailed description.

As the support of the light-sensitive material of the present invention, in addition to those described above, a support obtained by stretching a styrene polymer having a syndiotactic structure can be preferably used. This polymer support is similar to that described above,
It may be a homopolymer or a copolymer. Such a polymer support is described in detail in JP-A-8-220694.

[0090]

EXAMPLES The present invention will now be described specifically with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Method for Preparing Photosensitive Silver Halide Emulsion> Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] A well-stirred aqueous gelatin solution (16 g of gelatin in 540 ml of water, bromide Add 0.24 g of potassium, 1.6 g of sodium chloride and 24 mg of compound (a) and add 55 ° C.
(1) solution and (2) solution in Table 1 were simultaneously added at an equal flow rate for 19 minutes. After 5 minutes, (3) in Table 1
The solution and the solution (4) were simultaneously added at an equal flow rate for 24 minutes. After washing with water and desalting in a conventional manner, lime-treated ossein gelatin 1
7.6 g and 56 mg of compound (b) were added to adjust the pH to 6.
2. Adjust the pAg to 7.7 and add 0.41
g, and 1.02 mg of trimethylthiourea, and the mixture was optimally chemically sensitized at 60 ° C. After this, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.18
g, sensitizing dye (c) 64 mg, potassium bromide 0.41 g
Were added successively and then cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 59 having an average grain size of 0.30 μm was obtained.
0 g was obtained.

[0092]

[Table 1]

Photosensitive silver halide emulsion (2) [for green-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.30 g of potassium bromide, 2.0 g of sodium chloride and 2.0 g of compound (a ) Add 30mg and add 46mg
(1) solution and (2) solution of Table 2 were added simultaneously at an equal flow rate for 10 minutes. After 5 minutes, (3) in Table 2
The solution and the solution (4) were simultaneously added at an equal flow rate for 30 minutes. One minute after the completion of the addition of the solutions (3) and (4), 60 ml of a methanol solution of the sensitizing dye (including 360 mg of the sensitizing dye (d ₁ ) and 73.4 mg of the sensitizing dye (d ₂ )) was collectively added. Was added. After washing with water and desalting (using a sedimentation agent (e) at pH 4.0) in a conventional manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and the pAg to 7.6. , 1.8 mg of sodium thiosulfate, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene 18
0 mg was added, and the mixture was optimally chemically sensitized at 60 ° C. Next, 90 mg of antifoggant (f) and compound (b) as a preservative
After adding 70 mg and 3 ml of compound (g), the mixture was cooled. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0094]

[Table 2]

Photosensitive silver halide emulsion (3) [for blue-sensitive emulsion layer] A well-stirred aqueous gelatin solution (31.6 g of gelatin, 2.5 g of potassium bromide, and 13 mg of compound (a) in 584 ml of water) (Additionally heated to 70 ° C.), the addition of the liquid (2) in Table 3 was started first, and 10 seconds later, the addition of the liquid (1) was started. Thereafter, the liquids (1) and (2) were added over 30 minutes. (2) Five minutes after the completion of the addition of the solution, the addition of the solution (4) in Table 3 was further started, and 10 seconds later, the addition of the solution (3) was started. Solution (3) was added over 27 minutes and 50 seconds, and solution (4) over 28 minutes. After washing with water and desalting (using a sedimenting agent (j) at pH 3.9) in a conventional manner, 24.6 g of lime-treated ossein gelatin and 56 m of compound (b) were obtained.
g to adjust the pH to 6.1 and the pAg to 8.5,
0.55 mg of sodium thiosulfate was added, and the mixture was optimally sensitized at 65 ° C. Next, 0.35 g of sensitizing dye (h), 56 mg of antifoggant (i), and compound (g) as a preservative
After adding 2.3 ml, the mixture was cooled. Thus, a monodispersed octahedral silver bromide emulsion 58 having an average grain size of 0.55 μm was obtained.
2 g were obtained.

[0096]

[Table 3]

<Preparation method of zinc hydroxide dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed for 1 hour by a mill using glass beads. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Method for Preparing Emulsified Dispersion of Coupler> Table 4
The oil phase component and the water phase component having the compositions shown in
Make a homogeneous solution at 0 ° C. The oil phase component and the aqueous phase component were combined and dispersed in a 1-liter stainless steel container with a dissolver at 10,000 rpm for 20 minutes. to this,
As post-water addition, the amount of warm water shown in Table 4 was added, and 2000 r
Mix for 10 minutes at pm. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0099]

[Table 4]

Using the thus obtained raw materials, a heat-developable color light-sensitive material 101 having a multilayer structure shown in Table 5 was produced.

[0101]

[Table 5]

Next, as shown in Table 6, photosensitive materials 102 to 111 having exactly the same composition as the photosensitive material 101 except that the developing agents of the first layer and the third layer were changed, respectively, were prepared. FUJIXPICTROST
AT200 (manufactured by Fuji Photo Film Co., Ltd.) was mounted on a photosensitive material magazine, and B, G, and R filters having continuously changed densities were mounted on a slide enlarging unit, and subjected to heat development processing under standard conditions. At that time, the image receiving material used was an image receiving material containing a base generator described in Examples of JP-A-5-188554). When the image receiving material was peeled off after the processing, clear color images of cyan, magenta and yellow were obtained corresponding to the filters exposed on the light-sensitive material side. Immediately after processing, the highest concentration part (D
Table 7 shows the results of measuring the maximum density (max) and the minimum density part (Dmin) with an X-rite densitometer.

[0103]

[Table 6]

[0104]

[Table 7]

From the results shown in Table 7, first, the samples 101 to 1 containing the ordinary p-sulfonamidophenol-type active substance were used.
Compared with Comparative Example No. 03, the photosensitive materials 104 to 111 using the p-sulfonamidophenol-type main compound of the present invention have Dm
It can be seen that ax has greatly increased. From the above, the effect of the present invention is clear.

Example 2 Silver benzotriazole emulsion [organic silver salt] 28 g of gelatin and 13.2 g of benzotriazole were added to water 3
Dissolved in 00 ml. This solution was kept at 40 ° C. and stirred. A solution in which 17 g of silver nitrate was dissolved in 100 ml of water was added to this solution over 2 minutes. The pH of the benzotriazole silver emulsion was adjusted, sedimented, and excess salts were removed. Thereafter, the pH was adjusted to 6.30 to obtain 400 g of a silver benzotriazole emulsion.

Using the silver benzotriazole emulsion thus obtained, a heat-developable color light-sensitive material 20 shown in Table 8 was used.
1 was produced.

[0108]

[Table 8]

[0109]

[Table 9]

Next, as shown in Table 9, photosensitive materials 202 to 211 having exactly the same composition as 201 except that the developing agents of the first and third layers were changed, respectively. The B, G, and R wedges having continuously changed densities are passed through the photosensitive materials 201 to 211 formed as described above to form
Exposure was performed at 00lux for 1 second. This exposed sample
The substrate was heated for 10 seconds while being closely attached to a heat drum heated to 130 ° C. so that the back surface was in contact therewith. After the processing, when the light-sensitive material was peeled off from the heat drum, cyan, magenta, and yellow color images corresponding to the B, G, and R filters were clearly obtained on the light-sensitive material. Immediately after the processing, the highest density part (Dmax) and the lowest density part (Dmin) of this sample are determined by X-ri.
Tables 10 and 11 show the results measured by the TE densitometer. Further, the structural formula of the compound used in each of the above Examples is shown below,

[0111]

[Table 10]

[0112]

[Table 11]

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

From the results shown in Table 11, as in Example 1, the p-sulfonamidophenol-type principal compound of the present invention was used in comparison with the photosensitive materials 201 to 203 using the ordinary p-sulfonamidophenol-type principal compound. Photosensitive materials 204 to 211
It can be seen that Dmax is greatly increased as in Example 1. The effect of the present invention is clear from this embodiment.

[0122]

As demonstrated in the examples, the silver halide color photographic light-sensitive material and the image forming method according to the present invention have an effect of excellent dye formation efficiency.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Fumio Ishii 1 Konica Co., Ltd., Sakuracho, Hino-shi, Tokyo In-house F-term (reference) 2H016 AA00 BD00 BK00 BK02 2H023 AA00 CD06

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a color developing agent represented by the following general formula [1]. Embedded image [Wherein A is -OH, -OR ₁₁ , -NH ₂ , -NHR ₁₂
Or a group selected from —NR ₁₃ R ₁₄ , and R ₁₁ and R ₁₄
Represents an alkyl group or a substituted aryl group, and R ₁₂ and R ₁₃ represent a substituent. R _{1 to} R ₄ represent a hydrogen atom or a substituent,
Represents a group having a total Hammett substituent constant σp value of less than 0 and a total σm value of 0 or more. Ar is substituted;
Represents an unsubstituted aromatic group. The substituents of the aromatic group may be bonded to each other to form a ring. ] 2. The silver halide color photographic material according to claim 1, wherein Ar in the general formula [1] is an aromatic group having a substituent at the ortho position. 3. The silver halide color photographic material according to claim 1, wherein Ar in the general formula [1] is an ortho-substituted phenyl group. 4. In the general formula [1], _one of the substituents of R _{1 to} R ₃ has a ballast group of 8 or more, or the total number of carbon atoms of the substituent of Ar is 8 or more. The silver halide color photographic light-sensitive material according to any one of claims 1 to 3, characterized in that: 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the support contains at least a photosensitive silver halide, a binder and a coupler. 6. An image forming method comprising thermally developing the silver halide color photographic light-sensitive material according to claim 1 at 60 ° C. to 120 ° C.