JP2000035632A - Photographic sensitive material and its processing method and supporting body for this material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic sensitive material superior in sharpness and a little of residual dye stains, and further, short in processing time and capable of dry processing, and in addition, the supporting body for the photographic sensitive material superior in electrification characteristics. SOLUTION: This silver halide photographic sensitive material is characterized by incorporating photosensitive silver halide and at least one kind of fine particles of a metal or metal oxide characterized by having an absorbance at a wavelength attaining to the maximum absorbance in the region of 400-700 nm lower than the absorbance at 800 nm wavelength in a layer formed on the support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material having a sensitivity to infrared rays (hereinafter, sometimes simply referred to as a light-sensitive material or a light-sensitive material), a processing method thereof, and a support for the light-sensitive material. Is to provide a light-sensitive material and a processing method, in which the residual color stain is small, the processing time is short, or the dry processing is possible.
An object of the present invention is to provide a support for a photosensitive material having excellent charging characteristics.

[0002]

2. Description of the Related Art Upon exposure of a photographic light-sensitive material, incident light is reflected and refracted by silver halide and other additives and a layer interface, thereby blurring an image and degrading sharpness. To prevent this, so-called antihalation (A
H) Dyes and anti-irradiation (AI) dyes have been widely used. Conventionally, the performance required for AH and AI dyes is to absorb light of a desired wavelength, not to have an unnecessary effect on a silver halide emulsion, and to completely discolor or flow out during processing. No color was left on the surface.

[0003] In recent years, there has been a remarkable tendency for rapid processing and dry processing, and the problem of residual color stains in which coloring derived from dyes remains after the processing has increased, and improvements thereof have been strongly demanded. In particular, in the case of a so-called dry treatment in which no water is used for the treatment, no outflow of the dye can be expected at all, and the residual color stain tends to increase, so that improvement has been awaited.

[0004] A typical example of AI and AH dyes that can absorb infrared rays is an organic dye, and many compounds have been proposed.
Of these, cyanine dyes and oxonol dyes are particularly frequently used, but both have insufficient residual color stains, have poor stability, and have disadvantages of high cost.

[0005] Colloidal silver has been widely used in addition to organic dyes as a dye in which residual color stain hardly remains after processing. However, colloidal silver is bleached in the bleaching and fixing processes,
There are drawbacks such as a burden on the treatment due to the outflow, a high cost, and the use of a dry treatment that does not decolorize and cannot be used, and improvements have been awaited.

As a colloidal silver-related technique, Japanese Patent Application Laid-Open No. 9-310037 discloses a technique in which silver fine particles containing metals such as palladium, copper, and gold are used as a coating liquid for solar shading, and the coating liquid is applied. Although a post-heated film has been proposed, this technique is not a technique applicable to photographic light-sensitive materials because it is premised on heat treatment after coating.
Even when the heat treatment is omitted, the half width of absorption is large,
Since the residual color stain was large, it could not be applied to photographic materials. The specification does not describe nor suggest applying this technique to a photographic light-sensitive material.

[0007] Antimony-containing tin oxide (ATO) and indium-containing tin oxide (ITO), which are known as infrared absorbing materials composed of metal oxide fine particles, absorb far infrared rays well, but absorb little near infrared rays. The absorption was large, the residual color stain was large, and it could not be applied to photographic materials.

[0008] It is known to apply a metal oxide to a photosensitive material for the purpose of preventing static charge. For example, use of a tin oxide sol has been proposed. However, the tin oxide sol has a spectral absorption maximum wavelength of 1000 nm or more, has insufficient absorption of near-infrared rays, and has a visible portion, particularly 700 nm or 400 nm.
Absorption near, large residual color stain, AH, AI
It could not be used as a dye.

[0009] "Application of a sol-gel method - light, electrons, chemical, cold synthesis of biofunctional materials -" Sumio Sakka al, PbO-TiO ₂ based on 134 pages published Agne Shofusha and _Bi 2 _O 3 -Ti
Although it is described that the O ₂ -based film is a reflective film having almost no absorption in the visible region, its spectral reflection wavelength is not described, and it is described that the O ₂ -based film is applied to a silver halide photographic material. There is no description that suggests.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photographic light-sensitive material which is excellent in sharpness, has little residual color stain, has a short processing time, and can be dry-processed, and a processing method. Another object of the present invention is to provide a support for a photographic material having excellent charging characteristics.

[0011]

The above objects of the present invention are as follows. In a layer provided on the support, photosensitive silver halide,
And halogen containing at least one kind of metal or metal oxide fine particles, wherein the absorbance at a wavelength at which spectral absorption is maximum in the range of 400 nm to 700 nm is smaller than the absorbance at 800 nm. Silver photographic materials,

2. The layer provided on the support contains photosensitive silver halide and at least one kind of metal or metal oxide fine particles characterized in that the spectral absorption of the photosensitive material does not substantially change after processing. A silver halide photographic light-sensitive material,

3. 2. The heat-developable silver halide photographic material according to the above item 1, wherein the layer provided on the support contains an organic silver salt and a binder.

4. The layer provided on one side of the support contains photosensitive silver halide, and the layer provided on the other side contains fine particles of at least one metal or metal oxide. 3. The silver halide photographic material according to the above 1 or 2,

[0015] 5. In a layer provided on the support, an organic silver salt, a binder, a photosensitive silver halide, and 400 nm
Heat developing a photographic light-sensitive material containing at least one kind of metal or metal oxide fine particles, wherein the absorbance at a wavelength at which the spectral absorption is maximum at 700 nm or less is smaller than the absorbance at 800 nm. Characterized processing method,

6. In a layer provided on the support, an organic silver salt, a binder, a photosensitive silver halide, and 400 nm
Infrared photosensitivity comprising at least one kind of metal or metal oxide fine particles characterized in that the absorbance at a wavelength at which the spectral absorption is maximum at a wavelength of 700 nm or less is smaller than the absorbance at 800 nm. Photographic light-sensitive materials,

[7] In a layer provided on the support, an organic silver salt, a binder, a photosensitive silver halide, and 400 nm
A laser exposure photograph containing at least one kind of metal or metal oxide fine particles, wherein the absorbance at a wavelength at which the spectral absorption is maximum at 700 nm or less is smaller than the absorbance at 800 nm. Photosensitive material,

8. It contains at least one kind of fine particles of a metal or metal oxide, characterized in that the absorbance at the wavelength where the spectral absorption is maximum in the range from 400 nm to 700 nm is smaller than the absorbance at 800 nm. A support for a photographic light-sensitive material,

9. A layer provided on a support, wherein at least the photosensitive silver halide has an absorbance at a wavelength at which spectral absorption is maximum at 400 nm or more and 700 nm or less which is 以下 or less of an absorbance at 800 nm. A silver halide photographic light-sensitive material containing fine particles of one kind of metal or metal oxide,

[10] The layer provided on the support has a photosensitive silver halide and an absorbance of 800 nm at a wavelength at which spectral absorption is maximum at 400 nm or more and 700 nm or less.
At least one metal or metal oxide fine particle characterized by having a light absorbance of 1/10 or less.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The absorbance referred to in the present invention is the absorbance measured by transmitted light. In the present invention, the fine particles refer to particles having a sphere radius (hereinafter, also referred to as a converted radius) of 1000 μm or less when the average volume of the particles is converted into a sphere having the same volume. It is preferable that the fine particles have a reduced radius of 200 μm or less in terms of low light scattering, and the reduced radius is 100 μm.
Most preferably, it is not more than μm. In the present invention,
"Substantially no change in spectral absorption during processing" means that the absorbance at the maximum wavelength of spectral absorption changes by 5% or less before and after the processing.

The treatment method of the present invention is not particularly limited.
Processing using a solution such as -41 or thermal development may be used. It is more preferable to apply heat development in that processing can be performed in a short time without the need for preparation and management of a processing liquid. When a treatment with a solution is applied, a CPK-2-22 treatment manufactured by Konica Corporation or the like can be preferably applied in addition to the C-41 treatment. The development may be immersed in the processing solution in the tank,
The processing solution may be sprayed or applied to the photosensitive material.

The metal portion of the metal or metal oxide used in the present invention is not particularly limited, but is preferably a transition metal, and is preferably 1B, 2B, 5B, 6B, 7B, or 4B after the fourth period.
More preferably, it is a metal belonging to Group 8, 3A, 4A,
Most preferably, they are silver, gold, palladium, indium, lead, bismuth and titanium. The oxidation number of the metal oxide is not particularly limited, but is preferably the most stable oxidation number in the air among the possible oxidation numbers.

The metal or metal oxide fine particles of the present invention are more preferably fine metal particles. The metal or metal oxide fine particles of the present invention may contain a non-metal or non-metal element oxide in combination, and for example, titanium oxide containing silicon oxide can be used.

The method for preparing the metal or metal oxide fine particles of the present invention is not particularly limited, but can be prepared by a sol-gel method, can be prepared by reduction from a solution, and can be physically prepared by a disperser. Alternatively, the film can be formed by pulverization, and a film formed by vapor deposition can be separated from an object and dispersed. The sol-gel method is described in "Application of sol-gel method-light, electron,
Both low-temperature synthesis of chemical and biological functional materials-"and" Science of the sol-gel method-low-temperature synthesis of functional glass and ceramics-"both refer to the method described by Sakuhana S., published by Agne Shofusha. be able to.

The metal or metal oxide fine particles of the present invention can be added to any side of the support, but are preferably added to a side different from the emulsion. If necessary, it can be added to the support itself. The addition of the metal or metal oxide fine particles of the present invention to the light-sensitive material is advantageously performed by coating, and the metal or metal oxide fine particles of the present invention are mixed and applied as a binder such as gelatin or a polymer. Is preferred.

The present invention is preferably applied to a photosensitive material spectrally sensitized in the near-infrared region.
It is more preferable to apply the composition to a photosensitive material having an infrared sensitivity of 80 to 830 nm, since sharpness can be particularly greatly improved.

A heat-developable photosensitive material for forming a photographic image by using a heat-development processing method is disclosed, for example, in US Pat. No. 3,152,90.
No. 4, No. 3,457,075, and D.C. Morgan (M
organ) and B.C. "The Silver System Treated by Heat (Thermally)" by Shelly
Processed Silver System
s) "(Imaging Processes and Materials
Materials) Neblette Eighth Edition, Sturge, V.M. Wallworth
or)). Shepp Editing, 2nd
Pp. 1969).

The present invention can be preferably applied to a photosensitive material containing an organic silver salt. Organic silver salts are reducible silver sources, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (10 to 30, preferably 1 to 30).
An aliphatic carboxylate having 5 to 25 carbon atoms) and a nitrogen-containing heterocyclic salt are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research
ch Disclosure No. 17029 and 2996
3, which include: salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid,
Salts of palmitic acid, lauric acid, etc.); carboxyalkylthiourea salts of silver (eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl)-
Silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid) Acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiozoline-2-)
Thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole And silver salts of nitrogen acids and silver selected from benzotriazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferably, the silver source is silver behenate. The organic silver salt is preferably contained at a silver amount of 3 g / m ² or less. More preferably, it is 2 g / m ² or less.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound that forms a complex with silver.
Forward mixing method, reverse mixing method, simultaneous mixing method, JP-A-9-1276
The controlled double jet method described in No. 43 is preferably used.

The silver halide grains used in the present invention preferably have a small average grain size in order to suppress white turbidity after image formation and obtain good image quality, and more preferably have an average grain size of 0.20 μm or less. Is 0.03 μm
To 0.15 μm, particularly preferably 0.03 μm to 0.11 μm. The term "grain size" as used herein means the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains used in the present invention is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50%.
It is more preferably at least 70%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by the T.M. Tani, J .; Imaging Sc
i. , 29, 165 (1985).

The halogen composition of the silver halide grains used in the present invention is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. There may be. The photographic emulsion used in the present invention is P.I. Glaf
Chimieet Physique P.
photographique (Paul Montel)
G., 1967); F. Duffin's Pho
graphicalEmulsion Chemist
ry (The Focal Press, 1966)
Year), V. L. Ma by Zelikman et al
King and Coating Photogra
phy Emulsion (TheFocal Pr
ess, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Good. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of an organic silver salt and a halogen ion into silver halide, or by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, silver halide is 0.75 to organic silver salt.
Preferably, it is contained in an amount of 30% by weight. The silver halide used in the present invention includes one from Group 6 of the Periodic Table of the Elements.
It preferably contains an ion or a complex ion of a metal belonging to Group 0. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

One of these metal ions or complex ions may be used, or two or more of the same or different metals may be used in combination. The content of these metal ions or complex ions is generally from 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol per mol of silver halide, preferably from 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol. × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation. During the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added, as disclosed in JP-A-63-29603.
JP-A-2-306236, JP-A-3-167545, JP-A-4-76534, JP-A-6-110146, and JP-A-5-27
As described in, for example, No. 3683, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds are
It can be added by dissolving in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). For example, an aqueous solution of a metal compound powder or a metal compound and NaCl ,
A method in which an aqueous solution in which KCl is dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or as a third aqueous solution when the silver salt solution and the halide solution are simultaneously mixed. Adding silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or a method of preparing a metal ion or complex in advance during silver halide preparation. There is a method in which another silver halide grain doped with ions is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

When the present invention is applied to a photothermographic material, it is preferable to incorporate a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448 and 3,773.
No. 3,512, No. 3,593,863, and Res
Ear Disclosure No. 17029 and 2
9963, for example, the following can be mentioned. Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (e.g., 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone): tetrahydroquinoxalines (e.g., 1,2,3,4-tetrahydro Aminooxins; Azines (eg, a combination of an arylcarboxylic acid hydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids; A combination of a sulfonamide phenol; alpha-cyano-phenylacetic acid derivatives, bis -β-
Combinations of naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridine (for example, 2,6-dimethoxy) -3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-
Hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-
3-methylphenyl) propane, 4,5-ethylidene-
Bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0036]

Embedded image Wherein, R represents a hydrogen atom, R represents an alkyl group having 1 to 10 carbon atoms _(e.g., -C ₄ H _9, 2,4,4- trimethylpentyl), R 'and R "are C 1 -C To 5 alkyl groups (for example, methyl, ethyl, t-butyl).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0038]

Embedded image

The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × per mol of silver.
It is 10 ^-2 to 10 mol, particularly 1 × 10 ^{-2 to} 1.5 mol.

Binders suitable for the light-sensitive material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and poly (vinyl). Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate,
Poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile) , Copoly (styrene-butadiene), poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s, poly (urethane) s, phenoxy resins, poly (vinyldene chloride) , Poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amide) s. It may be hydrophilic or non-hydrophilic. In the present invention, the binder amount of the photosensitive layer is preferably 1.5 to 6 g / m ² . More preferably, it is 1.7 to 5 g / m ² .

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and a polymer matting agent or an inorganic matting agent is contained in a weight ratio of 0.5 to 10% with respect to all binders on the emulsion layer side. Is preferred. The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as the inorganic substance, silica described in Swiss Patent No. 330,158 and the like, and French Patent Nos. 1 and 2,
No. 96,995, glass powder described in British Patent No. 1,1
No. 73,181 or the like, alkaline earth metals or carbonates such as cadmium and zinc can be used as a matting agent. As organic substances, US Patent No. 2,322,0
No. 37, Belgian Patent No. 625,451
And starch derivatives described in British Patent No. 981,198, etc., polyvinyl alcohol described in JP-B-44-3643, etc., polystyrene or polymethacrylate described in Swiss Patent No. 330,158, U.S. Pat. Organic matting agents such as polyacrylonitrile described in 3,079,257 and the like and polycarbonate described in U.S. Pat. No. 3,022,169 can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following equation. (Standard deviation of particle size) / (Average value of particle size) × 100

The matting agent according to the present invention can be contained in any constituent layer. However, in order to achieve the object of the present invention, the matting agent is preferably a constituent layer other than the photosensitive layer, and more preferably from the support. The outermost layer to look at.

The method of adding the matting agent according to the present invention may be a method of dispersing in a coating solution in advance and applying the solution.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

The photosensitive material to which the present invention is applied can contain a hydrazine compound. Preferred hydrazine compounds used in the present invention include RESEARC
HDISCLOSURE Item 23516 (198
November, p. 346) and references cited therein, as well as U.S. Pat. Nos. 4,080,207 and 4,26.
9,929, 4,276,364, 4,27
8,748, 4,385,108, 4,45
9,347, 4,478,928, 4,56
0,638, 4,686,167, 4,91
2,016, 4,988,604, 4,99
4,365, 5,041,355, 5,10
No. 4,769, British Patent No. 2,011,391B, European Patent Nos. 217,310, 301,799 and 3
No. 56,898, JP-A-60-179834, and JP-A-60-17934.
-170733, 61-270744, 62-
No. 178246, No. 62-270948, No. 63-2
Nos. 9751, 63-32538, 63-1040
No. 47, No. 63-121838, No. 63-12933
No. 7, 63-223744, 63-234244
No. 63-234245, No. 63-234246
Nos. 63-294552 and 63-306438
No. 64-10233, JP-A-1-90439,
1-1100530, 1-1105594, 1-
No. 105943, No. 1-276128, No. 1-280
Nos. 747, 1-283548, 1-283549
No. 1-285940, No. 2-2541, No. 2-
77057, 2-153838, 2-1962
No. 34, No. 2-196235, No. 2-198440
No. 2-198441, No. 2-198442, No. 2-220042, No. 2-221953, and No. 2-2
No. 21954, No. 2-285342, No. 2-2853
No. 43, No. 2-289843, No. 2-302750
No. 2-304550, No. 3-37642, No. 3
-54549, 3-125134, 3-184
No. 039, No. 3-240036, No. 3-240037
No. 3-259240, No. 3-280038, No. 3-282536, No. 4-51143, No. 4-56
No. 842, No. 4-84134, No. 2-230233
No. 4-96053, No. 4-216544, No. 5
No. 455761, No. 5-45762, No. 5-4576
No. 3, 5-45764, 5-45765, 6
-289524 and 9-160164.

In the present invention, the amount of the hydrazine compound to be added is 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ per mol of silver.
^-1 mol is preferable, and the range of 1 × 10 ⁻⁵ mol to 5 × 10 ⁻² mol is particularly preferable.
The hydrazine compound of the present invention is used by dissolving in a suitable organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. be able to. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Things can be created and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used. In the present invention, it is preferable to use indazoles (for example, nitroindazole) as an antifoggant in combination with a hydrazine compound.

The photographic material of the present invention may contain a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative, or a hydroxyamine derivative, in combination with the hydrazine compound.

When the present invention is applied to a photothermographic material, the photosensitive material is stable at room temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure.
Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The light-sensitive material of the present invention has at least one light-sensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The light-sensitive material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

When the present invention is applied to a photothermographic material, a toning agent is preferably added. Examples of suitable toning agents are Research Disclosure No. 170
No. 29. Preferred toning agents are phthalazone or phthalazine.

The light-sensitive material of the present invention includes, for example,
No. 159841, No. 60-140335, No. 63-2
No. 31437, No. 63-259651, No. 63-30
Nos. 4242 and 63-15245, U.S. Pat.
39,414, 4,740,455, 4,74
1,966, 4,751,175, 4,83
Sensitizing dyes described in U.S. Pat. No. 5,096 can be used. Useful sensitizing dyes for use in the present invention are, for example, RESEARC
H DISCLOSURE Item17643IV-
Item A (December 1978, p. 23), Item 18
It is described in the literature described or cited in section 31X (August 1978, p. 437). JP-A-59-19
Tricarbocyanines described in JP-A-1032 and JP-A-60-80841; the general formula (IIIa) and the general formula (II) in JP-A-59-192242 and JP-A-3-67242;
Dicarbocyanines containing a 4-quinoline nucleus described in Ib) are advantageously selected. Further, the wavelength of the infrared laser light source is 750 nm or more, more preferably 800 n
m or more, in order to cope with a laser in such a wavelength range, Japanese Patent Application Laid-Open Nos.
No. 1432, Tokuhei 6-52387, No. 3-1093
No. 1, U.S. Pat. No. 5,441,866, JP-A-7-1
Sensitizing dyes described in No. 3295, etc. are preferably used. These sensitizing dyes may be used alone,
Combinations thereof may be used, and combinations of sensitizing dyes are often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The exposure of the light-sensitive material of the present invention is not particularly limited, but exposure with an infrared semiconductor laser is preferred.

[0054]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. Example 1 (Preparation of Silver Fine Particle Dispersion) An aqueous gelatin solution and an aqueous dodecylsulfonic acid solution were added to silver powder manufactured by Kanto Chemical Co., Ltd., and pulverized using a ball mill for 24 hours to obtain silver fine particles having an average particle diameter of 40 nm. This was designated as Dispersion 102.

(Preparation of silver halide grains) 900 m of pure water
After dissolving 7.5 g of gelatin and 10 mg of potassium bromide in 1 l and adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and potassium bromide in a molar ratio of (96/4) were added. The aqueous solution containing potassium iodide was pAg
It was added over 10 minutes by the controlled double jet method while maintaining at 7.7. Then 4-hydroxy-6
0.3 g of methyl-1,3,3a, 7-tetrazaindene
Was added, and the pH was adjusted to 5 with NaOH to give an average particle size of 0.06 μm, a variation coefficient of projected diameter area of 8%, and
Cubic silver iodobromide grains having a 0% face ratio of 86% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, followed by addition of 0.1 g of phenoxyethanol, pH 5.9, pA
g was adjusted to 7.5. Thereafter, sensitizing dye SD-1 was added at 5 × 10 ⁻⁵ mol per mol of silver halide, and 2- (4-chlorobenzoyl) benzoic acid was added at 0.44 g / m ² . Thereafter, the temperature was raised to 60 ° C., 2 mg of sodium thiosulfate was added, the mixture was aged for 100 minutes, and then cooled to 38 ° C. to complete the chemical sensitization to obtain silver halide grains.

(Preparation of Organic Fatty Acid Silver Emulsion) 300 ml of water
10.6 g of behenic acid was put therein, dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was sufficiently stirred.
Was added and left as it was for 1 hour. Then 3
After cooling to 0 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, the silver halide grains prepared at 40 ° C. were adjusted to 10 mol% as silver based on the behenic acid.
While stirring while heating. Further, 25 ml of a 1N aqueous solution of silver nitrate was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

To the emulsion, polyvinyl butyral dissolved in ethyl acetate was added, stirred sufficiently, and allowed to stand, to separate into an ethyl acetate phase containing silver behenate grains and silver halide grains and an aqueous phase. After removing the aqueous phase, silver behenate grains and silver halide grains were collected by centrifugation. Thereafter, 20 g of synthetic zeolite A-3 (sphere) manufactured by Tosoh Corporation and 22 ml of isopropyl alcohol were added, and the mixture was allowed to stand for 1 hour and filtered. Further, 3.4 g of polyvinyl butyral and 23 ml of isopropyl alcohol were added, and the mixture was sufficiently stirred and dispersed at 35 ° C. at a high speed to complete the preparation of the organic fatty acid silver emulsion.

(Composition of photosensitive layer) Silver emulsion of organic fatty acid 1.75 g (in silver) / m ² pyridinium hydrobromide perbromide 0.07 g / m ² Calcium bromide 0.05 g / m ^{2 2} -mercapto-5-methylimidazole 0.04 g / m ² tribromomethylsulfonylquinoline 0.36 g / m ² hexamethylene diisocyanate 0.16 g / m ² phthalazine 0.30 g / m ² 4-methylphthalic acid 0.14 g / m ² tetrachlorophthalic acid 0.10 g As the / m ² solvent, methyl ethyl ketone, acetone, and methanol were appropriately used.

(Surface Protection Layer Composition) A surface protection layer coating solution was prepared as follows. ^3. Cellulose acetate 2.3 g / m ² polymethyl methacrylate (particle size 10 μm) 0.02 g / m ² 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 8 × ¹⁰ in the -3 mol / ^{m 2} dye 1 0.024 g / ^{m 2} benzotriazole 0.021 g / ^{m 2} of silicon dioxide (particle size 2μm) 0.22g / ^{m 2} solvent, methyl ethyl ketone, for acetone, methanol appropriately Was.

(Composition of Backing Layer) A coating solution for the backing layer was prepared as follows. Cellulose acetate 4g / ^{m 2} Dye 1 0.019 g / ^{m 2} Polymethyl methacrylate (particle size 10μm) 0.02g / ^{m 2}

Thickness 1 biaxially stretched with the above composition
A sample 101 was prepared by applying the film to a 75 μm polyethylene terephthalate film and drying the film. Sample 102 was prepared in the same manner as Sample 101 except that Dye 1 of Sample 101 was changed to Dispersion 102. Dispersion 102 was added in an amount of 8
The absorbance at 10 nm was adjusted to be the same as that of Sample 101.

Samples 103 and 104 were prepared in the same manner as in Sample 101 except that a dispersion of anatase-type titanium dioxide and black colloidal silver were added so that the absorbance at 810 nm was the same as that of Sample 101.

The photothermographic materials 101, 102,
Each of 103 and 104 was processed to a half-cut size, and a 810 nm laser diode was exposed to a beam inclined by 13 ° from a vertical plane. Thereafter, heat development was performed at 120 ° C. for 15 seconds using a heat drum, and samples 111, 112, 113,
And 4.

[0064]

Embedded image

"Evaluation of Sharpness" Samples 111, 112, 1
MTF of 13/114 at 10 lines / mm was measured,
The sharpness was evaluated. Table 1 shows the results.

"Evaluation of residual color stain" Samples 111 and 11
The residual color stains of 2, 113 and 114 were visually compared. The evaluation was made by subjective evaluation using 10 monitors. The total score was 3 points where there was no practical problem and there were practical problems. Was compared. Table 1 shows the results.

[0067]

[Table 1]

Table 1 shows that the sample of the present invention has good sharpness.
It can be seen that there is little residual color stain. In the sample 113 using titanium oxide and the sample 114 using colloidal silver, light scattering in the visible part and residual color stain were large, and thus had no commercial value.

Example 2 In order to compare the difference in the residual color stain due to the difference in the processing method, the photosensitive materials 101, 102, 103, and 10 of Example 1 were compared.
Sample No. 4 was subjected to liquid treatment by Kodak Co., Ltd. C-41 treatment, and samples 121, 122, 123 and 124 were evaluated for residual color stain in the same manner as in Example 1 and compared with the sample of Example 1. Table 2 shows the results.

[0070]

[Table 2]

From Table 2, it can be seen that the comparative sample had the residual color stain deteriorated by the heat development, whereas the sample of the present invention had the residual color stain not deteriorated by the heat development, which is preferable. Example 2 shows that the present invention shows a remarkable effect when applied to thermal development.

Example 3 Dye 1 added to backing layer in Example 1
Was stopped and instead added to the polyester support such that the coverage per unit area was equal. The dye was added by mixing and kneading the polyester when the polyester was melted for biaxial stretching of the polyester, and biaxially stretching the same as in Example 1 to form a support.

Photosensitive materials 301, 302, 303 and 304 were prepared in the same manner as in Example 1 except that this support was used. These samples were exposed and thermally developed in the same manner as in Example 1,
Samples 311, 312, 313, and 314 were obtained. Example 1
The remaining color stain and the sharpness were evaluated in the same manner as in Example 1 and compared with the sample of Example 1. Table 3 shows the results.

[0074]

[Table 3]

As shown in Table 3, the sharpness of the sample 312 in which the dye of the present invention was added to the support was more preferable than that of the sample 112 in which the dye was added to the backing layer, and the residual color stain was not deteriorated. Although some samples have improved, the residual color stain has deteriorated in all samples,
Not preferred. From Example 3, it can be seen that the technique of the present invention shows a remarkable effect when applied to a support.

[0076]

According to the present invention, it is possible to provide a photographic light-sensitive material and a processing method which have a small residual color stain, a short processing time, and can be dry-processed. A support for a photosensitive material can be provided.

Claims (10)

[Claims] 1. A layer provided on a support, comprising: a photosensitive silver halide; and an absorbance at a wavelength at which spectral absorption is maximum at 400 nm or more and 700 nm or less is smaller than an absorbance at 800 nm. A silver halide photographic material comprising at least one kind of metal or metal oxide fine particles. 2. A method according to claim 1, wherein the layer provided on the support comprises a photosensitive silver halide and at least one metal or metal oxide, wherein the spectral absorption of the photosensitive material does not substantially change after processing. A silver halide photographic material comprising fine particles. 3. The heat-developable silver halide photographic material according to claim 1, wherein the layer provided on the support contains an organic silver salt and a binder. 4. A layer provided on one side of the support contains photosensitive silver halide, and a layer provided on the other side contains fine particles of at least one metal or metal oxide. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein: 5. A layer provided on a support, comprising an organic silver salt, a binder, a photosensitive silver halide and 400 nm or more.
Photothermographic material containing at least one kind of metal or metal oxide fine particles, characterized in that the absorbance at the wavelength where the spectral absorption is maximum below 00 nm is smaller than the absorbance at 800 nm. And the processing method. 6. A layer provided on a support, comprising an organic silver salt, a binder, a photosensitive silver halide and 400 nm or more.
An infrared-sensitive photograph containing at least one kind of fine particles of a metal or a metal oxide, wherein the absorbance at a wavelength at which spectral absorption is maximum at or below 00 nm is smaller than the absorbance at 800 nm. Photosensitive material. 7. A layer provided on a support, comprising an organic silver salt, a binder, a photosensitive silver halide, and 400 nm or more.
Photosensitivity for laser exposure comprising at least one kind of fine particles of metal or metal oxide, characterized in that the absorbance at a wavelength at which spectral absorption is maximum at or below 00 nm is smaller than the absorbance at 800 nm. material. 8. At least one kind of metal or metal oxide fine particles characterized in that the absorbance at a wavelength at which spectral absorption is maximum in the range of 400 nm to 700 nm is smaller than the absorbance at 800 nm. Support for a photographic material. 9. A layer provided on a support, comprising: a photosensitive silver halide; and an absorbance at a wavelength at which spectral absorption is maximum in a range from 400 nm to 700 nm is not more than 1/2 of an absorbance at 800 nm. At least one characterized by:
A silver halide photographic material containing fine particles of a metal or a metal oxide. 10. A layer provided on a support, wherein a light-sensitive silver halide and an absorbance at a wavelength at which spectral absorption is maximum in a range of 400 nm to 700 nm is 1/10 or less of an absorbance at 800 nm. A silver halide photographic material comprising at least one kind of metal or metal oxide fine particles.