JP2000095958A - Silver halide emulsion, silver halide photographic material, and heat-developable photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic material containing an infrared-sensitive silver halide emulsion layer showing high sensitivity and low fogging by using a silver halide emulsion containing at least one member selected among a plurality of compounds each having a specified structure. SOLUTION: There is provided a photosensitive silver halide emulsion containing at least one member selected from among compounds represented by formulae II and II, such as a compound represented by formula I. There is also provided a silver halide photographic material composed of a support and at least one layer of the photosensitive silver halide emulsion and at least one hydrophilic non-sensitive layer formed on the support. In the formulae, Y1, Y2, and Y11 are each oxygen, sulfur, selenium, or -CH=CH-; L1 to L9, and L11 to L16 are each methine; R1, R2, R11, and R12 are an aliphatic group; R3, R4, R13 and R14 are each an alkenyl, a cycloalkyl, or a heterocyclic group; W1, W2, W3, W4, W11, W12, W13, and W14 are each hydrogen, a substituent, or a nonmetallic atom required to form a fused ring between W1 and W2, W3 and W4, W11 and W12, or W13 and W14; X1, X11, K1, and K11 are each an ion which counterbalances the intramolecular charge; m1 is 0 or 1; and n1, n11, are each 0, 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, and more particularly to a photographic material and a photothermographic material using an infrared-sensitive silver halide emulsion having high sensitivity and low fog. It relates to the infrared photosensitive dye used.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is produced using silver halide fine particles having excellent characteristics such as high photosensitivity, memory, and high S / N characteristics.

However, since the photosensitive region of silver halide grains has a short wavelength near 500 nm and has a long wavelength end, spectral sensitization using a dye is indispensable for exposing to a longer wavelength. In particular, in recent years, with the development of light sources, photosensitive materials sensitive to infrared laser wavelengths have become increasingly important in industrial recording materials. Also, among the photographic recording photosensitive materials, infrared light-sensitive materials which are excellent in use for recording environmental information or improving the delineation ability have been receiving attention.

Many dyes used for this purpose have been known in the art. For example, T. James, "The Theory of the Photographic Process", 4th edition (1977, Macmillan) Co., N.
Y. ) P. 194-234, "The Cyanine Soy and Related Compounds" by Francis M. Harmer (1964, John Willy and
Sands, N. Y. ), Dem Stammer, "The Chemistry of Heterocyclic Compounds, Vol. 30," p. 441- (1977, John Willy and Sons, NY);
No. 38, No. 3-163440, No. 5-72660,
5-72661, 5-88292, 8-19
No. 4282, No. 9-166844, No. 9-28163
No. 1, No. 9-292672, No. 9-292673,
Nos. 10-73900 and U.S. Pat.
No. 4,900, No. 3,582,344, No. 4,5
Nos. 36,473, 4,740,455, 4,
Nos. 835,096, 5,393,654, UK Patent 774,779, EP 042002,
Various dyes such as cyanine dyes and merocyanine dyes described in the specification of 0821811 and the like are known.

[0005] These spectral sensitizing dyes must not only extend the photosensitive wavelength range of the silver halide emulsion but also satisfy the following conditions.

1) Spectral sensitization range is appropriate 2) Spectral sensitization efficiency is high 3) Between other additives such as stabilizers, antifoggants, coating aids, high boiling solvents, etc. 4) No adverse effect on the characteristic curve such as fogging or gamma change 5) When a silver halide photographic light-sensitive material containing a photosensitive dye is aged (especially at high temperature and high humidity) 6) Do not change the photographic performance such as fog during storage under the conditions. 6) The added photosensitive dye does not diffuse to layers in different photosensitive wavelength ranges to cause color turbidity. 7) Develop and fix. The pigment does not come off and cause color contamination.

[0007] However, the spectral sensitizing dyes disclosed hitherto have not yet reached a level which sufficiently satisfies all of these conditions. In particular, dyes having a maximum absorption in the infrared region have long conjugate chains and are easily affected by the environment, or the distance between the lowest vacant level and the highest occupied level is narrow and the conduction band level of silver halide grains is small. Since the lowest vacant level and the highest occupied level are close to each other, fogging is easily generated, and the sensitivity is lowered. Accordingly, an infrared-sensitive silver halide emulsion having high sensitivity, low fog, and little change in performance even with time has been desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide light-sensitive material having an infrared-sensitive silver halide emulsion layer having high sensitivity and low fog. An object of the present invention is to provide an infrared-sensitive, heat-developable silver halide photographic material which maintains high sensitivity and low fog even when it is used.

[0009]

The above objects of the present invention have been attained by the following constitutions.

[0010] 1. A silver halide emulsion comprising at least one compound represented by the following general formula [1] or [2].

[0011]

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(In the general formulas [1] and [2],
Y ₁ , Y ₂ and Y ₁₁ each represent an oxygen atom, a sulfur atom, a selenium atom or a —CH ＝ CH— group, and L _{1 to} L ₉ and L ₁₁
To L ₁₅ each represent a methine group. R ₁ , R ₂ , R ₁₁ and R
₁₂ represents an aliphatic group, and R ₃ , R ₄ , R ₁₃ and R ₁₄ each represent an alkenyl group, a cyclic alkyl group or a heterocyclic group.

W ₁ , W ₂ , W ₃ , W ₄ , W ₁₁ , W ₁₂ , W ₁₃ and W ₁₄ are each a hydrogen atom, a substituent, or W ₁ and W ₂ , W
Represents a group of nonmetallic atoms necessary for forming a condensed ring by bonding between ₃ and W ₄ , W ₁₁ and W ₁₂ , and W ₁₃ and W ₁₄ . X ₁ and X
₁₁ each represents an ion required to cancel the charge in the molecule, and k1 and k11 each represent the number of ions required to cancel the charge in the molecule. m1 represents 0 or 1, and n
1, n11 and n12 each represent 0, 1 or 2. However, n11 and n12 do not become 0 at the same time. ) 2. A silver halide emulsion comprising at least one compound represented by the following general formula [3] or [4].

[0014]

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(In the general formulas [3] and [4],
Y ₂₁ , Y ₂₂ and Y ₃₁ each represent an oxygen atom, a sulfur atom, a selenium atom or a —CH ＝ CH— group, and L _{21 to} L ₂₉ ,
L _{31 to} L ₃₅ each represent a methine group. R ₂₁ , R ₂₂ , R ₃₁
And R ₃₂ each represent an aliphatic group.

R ₂₃ , R ₂₄ , R ₃₃ and R ₃₄ each represent a group selected from an ethenyl group, a cyclopropyl group and a cyclobutyl group, and are represented by W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ , W ₃₁ , W ₃₂ , W ₃₃
And W ₃₄ are each a hydrogen atom, a substituent, or a bond required between W ₂₁ and W ₂₂ , W ₂₃ and W ₂₄ , W ₃₁ and W ₃₂ , W ₃₃ and W ₃₄ to form a fused ring Represents a non-metallic atomic group.
X ₂₁ and X ₃₁ each represent an ion required to cancel an intramolecular charge, and k21 and k31 each represent the number of ions required to cancel an intramolecular charge. m21 represents 0 or 1, and n21, n31 and n32 each represent 0, 1 or 2. However, n31 and n32 do not become 0 at the same time. ) 3. In a silver halide light-sensitive material having at least one hydrophilic non-light-sensitive layer and a light-sensitive silver halide emulsion layer on a support, at least one of the above-mentioned 1 and 2 3. A silver halide light-sensitive material comprising the silver halide emulsion according to any one of 2.

4. Organic silver salts, photosensitive silver halide grains,
A photothermographic material comprising a reducing agent and at least one of the compounds represented by formulas [1] to [4].

5. A compound represented by the general formula [3] or [4].

Hereinafter, the present invention will be described in detail.

Some of the above-mentioned techniques disclosed so far have the intention of avoiding the above-mentioned drawbacks by means of enhancing the adsorption of the photosensitive dye on the surface of the silver halide grains. Among them, alkylthio group in the dye molecule,
Those having a thioether group such as an arylthio group are known. It is thought that the substitution of a group having a high affinity for silver ions aims to increase the adsorptive power and improve the above-mentioned drawbacks. However, a compound which sufficiently satisfies the above conditions has not yet been obtained.

The present invention is different from the above-mentioned groups in that it is substituted with an alkenylthio group, a cyclic alkylthio group or a heterocyclic thio group. The present inventors have found that the above-mentioned disadvantages are greatly improved by this, and have led to the present invention.

It is unclear why the use of the dye of the present invention provides an infrared-sensitive material having higher sensitivity, lower fog, and superior storage stability over time as compared with conventional ones. Thus, the present inventors think. Although the thioether group certainly increases the affinity for the silver halide grain surface, the interaction between the dye molecules when J-aggregated and adsorbed on the silver halide surface is more likely to occur for the substituent having π-electronity than for the alkyl alone. We believe that it will strengthen and, as a result, contribute to increasing the attraction force.

Further, regarding the cycloalkyl group, it is considered that the group that maintains the planar structure contributes to controlling the intermolecular fluctuation when the dye forms an aggregate to facilitate the formation of a stacking structure. ing.

From such a viewpoint, it is considered that a chain alkyl group does not have such an effect, and an aryl group has a large group itself. Accordingly, relatively small alkenyl groups in the invention are preferred, and particularly preferred are vinyl, 2-propenyl and 3
-Butenyl group and the like, and a cycloalkyl group having a low degree of conformational freedom is preferable, and a cyclopropyl group, a cyclobutyl group and a cyclopentyl group are preferable.

In the present invention, the infrared-sensitive silver halide emulsion is a silver halide emulsion having sensitivity to light having a wavelength other than 400 to 700 nm in the visible region. The photosensitive wavelength of the silver halide emulsion is preferably from 700 nm to 900 nm, more preferably from 780 nm to 850 nm.
In the present invention, an infrared-sensitive silver halide light-sensitive material is a light-sensitive material that forms a black-and-white image by developing, fixing, and washing, and a developing, bleach-fixing, and washing process in which an emulsion layer contains a coupler, a colored coupler, and a DIR compound. Is a photosensitive material that forms a color image, or a heat-developable photosensitive material that is not wet-processed.

The sensitizing dyes represented by the general formulas [1] to [4] will be described. R ₁ , R ₂ , R ₁₁ , R ₁₂ , R ₂₁ ,
Examples of the aliphatic group represented by R ₂₂ , R ₃₁ and R ₃₂ include, for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group) , A pentyl group, an i-pentyl group, a 2-ethyl-hexyl group, an octyl group, a decyl group, etc.), having 3 to 3 carbon atoms.
10 alkenyl groups (for example, 2-propenyl group, 3-
A butenyl group, a 1-methyl-3-propenyl group, a 3-pentenyl group, a 1-methyl-3-butenyl group, a 4-hexenyl group, etc., an aralkyl group having 7 to 10 carbon atoms (for example, a benzyl group, a phenethyl group) Etc.). The groups described above further include a lower alkyl group (eg, a methyl group,
Ethyl group, propyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), vinyl group, aryl group (eg, phenyl group, p-tolyl group, p-bromophenyl group, etc.), trifluoro Methyl group, alkoxy group (for example, methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (for example, phenoxy group, p
-Tolyloxy group, etc.), cyano group, sulfonyl group (for example, methanesulfonyl group, trifluoromethanesulfonyl group, p-toluenesulfonyl group, etc.), alkoxycarbonyl group (for example, ethoxycarbonyl group, butoxycarbonyl group, etc.), amino group ( For example, an amino group, a biscarboxymethylamino group, an aryl group (eg, a phenyl group, a carboxyphenyl group, etc.), a heterocyclic group (eg, tetrahydrofurfuryl, 2-pyrrolidinone-1-)
Yl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), ureido group (eg, ureido group, 3-methylureide group, 3-phenylureido group, etc.), thioureido group (eg, thioureido group, 3- Methylthioureido group, etc., alkylthio group (eg, methylthio, ethylthio group, etc.), arylthio group (eg, phenylthio group, etc.), heterocyclic thio group (eg, 2-thienylthio group, 3-thienylthio, 2-imidazolylthio group, etc.) ),
Carbonyloxy group (eg, acetyloxy group, propanoyloxy group, benzoyloxy group, etc.), acylamino group (eg, acetylamino, benzoylamino group, etc.), thioamide group (eg, thioacetamido group, thiobenzoylamino group, etc.) Groups, or, for example,
Sulfo group, carboxy group, phosphono group, sulfate group, hydroxy group, mercapto group, sulfino group, carbamoyl group (for example, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (for example, , A sulfamoyl group,
N, N-3-oxapentamethyleneaminosulfonyl group, etc.), sulfonamide group (eg, methanesulfonamide, butanesulfonamide group, etc.), sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl group, etc.) ), An acylaminosulfonyl group (eg, acetamidosulfonyl, methoxyacetamidosulfonyl group, etc.), an acylaminocarbonyl group (eg, acetamidocarbonyl,
A methoxyacetamidocarbonyl group) or a sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl, ethanesulfinylaminocarbonyl group, etc.). Specific examples of the aliphatic group in which these hydrophilic groups are substituted include carboxymethyl, carboxyethyl, carboxybutyl, carboxypentyl, 3-sulfatobutyl, 3
-Sulfopropyl, 2-hydroxy-3-sulfopropyl group, 4-sulfobutyl, 5-sulfopentyl, 3-sulfopentyl, 3-sulfinobutyl, 3-phosphonopropyl, hydroxyethyl, N-methanesulfonylcarbamoylmethyl, 2-carboxy-2-propenyl,
Each group includes o-sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl and the like.

The alkenyl groups represented by R ₃ , R ₄ , R ₁₃ and R ₁₄ are, for example, 2-propenyl, 3-alkenyl
Butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group and the like. Examples of the cyclic alkyl group include, for example, cyclopropyl group, cyclopentyl group, and cyclohexyl. And the like. Examples of the heterocyclic group include groups such as a 2-thienyl group, a 3-thienyl group, and a 1-methyl-2-imidazolyl group. Each of these groups is a lower alkyl group (for example, Methyl group, ethyl group, etc.), lower alkoxy group (eg, methoxy group, ethoxy group, etc.), hydroxy group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), aryl group (eg, phenyl group) , Tolyl group, chlorophenyl group, etc.), mercapto group,
A group such as a lower alkylthio group (eg, a methylthio group, an ethylthio group, etc.) can be substituted.

W _{1 to} W ₄ , W _{11 to} W ₁₄ , W _{21 to} W ₂₄ , W ₃₁
To W ₃₃ and W ₃₄ , each of the substituents is specifically
Alkyl group (for example, methyl group, ethyl group, butyl group,
i-butyl group, etc.), aryl group (including monocyclic and polycyclic, for example, phenyl group, naphthyl group, etc.), heterocyclic group (eg, thienyl, furyl, pyridyl, carbazolyl, pyrrolyl, indolyl, etc.) Group), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), vinyl group, aryl group (eg, phenyl group, p-tolyl group, p-bromophenyl group, etc.), trifluoromethyl group, alkoxy group (E.g., methoxy, ethoxy,
Methoxyethoxy group etc.), aryloxy group (for example,
Phenoxy group, p-tolyloxy group, etc.), sulfonyl group (eg, methanesulfonyl group, p-toluenesulfonyl group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), amino group (eg, amino group) , Biscarboxymethylamino group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.), heterocyclic group (eg, tetrahydrofurfuryl, 2-pyrrolidinone-1-yl group, etc.), acyl group (eg, acetyl group) Groups, benzoyl groups, etc.), ureido groups (eg, ureido groups, 3-methylureido groups, 3-phenylureido groups, etc.), thioureido groups (eg, thioureido groups, 3-methylthioureido groups, etc.), alkylthio groups (eg, Methylthio, ethylthio groups, etc.), arylthio groups (for example, Niruchio group), a hydroxy group, a styryl group, and the like.

These groups can be substituted with the groups described in the description of the aliphatic group represented by R _{1 and the} like. Specific examples of the substituted alkyl group include, for example, 2-methoxyethyl, 2-hydroxyethyl, 3-ethoxycarbonylpropyl, 2
-Carbamoylethyl, 2-methanesulfonylethyl,
3-methanesulfonylaminopropyl, benzyl, phenethyl, carboxymethyl, carboxyethyl, allyl,
Examples of the substituted aryl group include, for example, p-carboxyphenyl, pN, N-dimethylaminophenyl, p-morpholinophenyl, and p-methoxyphenyl. , 3,4-dimethoxyphenyl, 3,4-methylenedioxyphenyl, 3-chlorophenyl, p-nitrophenyl, and the like. Specific examples of the substituted heterocyclic group include, for example, 5-chloro. -2-pyridyl, 5-ethoxycarbonyl-2-pyridyl, 5-carbamoyl-2-pyridyl and the like. W ₁ and W _2, W ₃ and W _4, W ₁₁ and W
_12, W ₁₃ and W _14, W ₂₁ and W _22, W ₂₃ and W _24, W ₃₁ and W ₃₂
Examples of the condensed ring which can be formed by connecting R ₃₃ and R ₃₄ to each other include a 5- or 6-membered saturated or unsaturated condensed carbocyclic ring. Any of these condensed rings can be substituted at any position, and examples of these substituted groups include the groups described above as the groups that can be substituted with the aliphatic group.

In the above general formulas [1] to [4], L ₁ to
L _9, L ₁₁ methine groups represented by _{~L 15, L 21 ~L 29,} L 31 ~L 35 each represents a substituted or unsubstituted methine group independently. Specific examples of the substituted group include a substituted or unsubstituted lower alkyl group (eg, methyl group, ethyl group, i-propyl group, benzyl group, etc.) and an alkoxy group (eg, methoxy group, ethoxy group, etc.). An aryloxy group (eg, phenoxy group, naphthoxy group, etc.), an aryl group (eg, phenyl group, naphthyl group, p-tolyl group, o-carboxyphenyl group, etc.), -N (V ₁ )
(V _2), - SR or Hajime Tamaki (e.g., 2-thienyl, 2-furyl, N, N'-bis (methoxyethyl)
Barbituric acid group). Here, R represents a lower alkyl group, an aryl group or a heterocyclic group as described above;
₁ and V ₂ each represent a substituted or unsubstituted lower alkyl group or aryl group, and V ₁ and V ₂ are
A 6-membered or 6-membered nitrogen-containing heterocycle can also be formed. In addition, the methine group can form a 5-membered or 6-membered ring by linking to methine groups adjacent to each other or to a methine group separated by one.

In the compounds represented by the above general formulas [1] to [4], when a group having a cationic or anionic charge is substituted, an equivalent amount of the compound is used so that the intramolecular charge is offset. A counter ion is formed by an anion or a cation. For example, specific examples of the cation necessary for canceling the intramolecular charge represented by X ₁ , X ₁₁ , X ₂₁ and X ₃₁ include a proton, an organic ammonium ion (for example, triethylammonium, Each ion such as triethanolammonium) and inorganic cations (for example, respective cations such as lithium, sodium and potassium). Specific examples of the acid anion include, for example,
Halogen ion (for example, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion, sulfate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonic acid ion, trifluorofluoride Methanesulfonate ion and the like.

The following are representative examples of the photosensitive dyes represented by the above general formulas [1] to [4], but the present invention is not limited to these compounds.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The above-mentioned infrared photosensitive dye is described in, for example, FM Hammer, The Chemistry of H.
eterocyclic Compounds No. 18
Volume, The Cyanine Dyes and Re
lated Compounds (A. Weisshe
rger ed. Published by Interscience, Ne
w York 1964), JP-A-3-13838.
No. 10-73900, Tokuhyo Hei 9-510022
No. 2,734,900, UK Patent No. 77
It can be easily synthesized by the method described in US Pat. No. 4,779.

Hereinafter, a method for synthesizing the compound according to the present invention will be specifically described.

Synthesis Example: Compound No. Synthesis of 7 2-methyl-5-vinylthiobenzothiazole 10.4
g and p-toluenesulfonic acid ethyl ester 12.0 g
And heated and stirred in an oil bath at 120 ° C. for 2 hours. Acetone was added to the reaction product, and the mixture was heated to reflux and allowed to cool, and the crystallized product was collected by filtration. 2.1 g of the isolated quaternary salt and 2,7-dimethoxy-
0.5 g of 1,4,5,8-tetrahydronaphthalene was mixed with 5 ml of dimethyl sulfoxide, and the mixture was heated and stirred in an oil bath at 120 ° C. for 5 minutes. Next, it was dissolved in methanol (20 ml), triethylamine (1 g) was added, and the mixture was heated and refluxed on a water bath for 20 minutes. After cooling, the precipitated crystals were collected by filtration and recrystallized from methanol to obtain 0.45 g of the desired product. It showed an absorption maximum at 756 nm (ε = 234,000) in a methanol solution.

The photosensitive dye of the present invention may be used alone, or two or more photosensitive dyes may be used in combination. When the sensitizing dyes of the present invention are used alone or in combination, the total of 1 × 10 ^-6 mol to 5 × 10 ^-3 mol, preferably 1 × 10 ^-3 mol, per mol of silver halide is obtained.
10 ⁻⁵ mol to 2.5 × 10 ⁻³ mol, more preferably 4 ×
It is contained in the silver halide emulsion at a ratio of 10 ⁻⁵ mol to 1 × 10 ⁻³ mol. When two or more photosensitive dyes are used in combination in the present invention, the photosensitive dyes can be contained in the silver halide emulsion at any ratio. The photosensitive dye of the present invention can be directly dispersed in an emulsion. Also, these are firstly suitable solvents such as methyl alcohol, ethyl alcohol, n-propanol, methyl cellosolve, acetone,
It can be dissolved in water, pyridine or a mixed solvent thereof and added to the emulsion in the form of a solution. Ultrasound can also be used for lysis. As a method for adding the photosensitive dye, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, etc., by dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to the emulsion; US Pat. JP-A-51-74624 discloses a method of dissolving a dye in a surfactant and adding the solution to an emulsion; using a compound for shifting to a longer wavelength side as described in JP-A-51-74624. And dissolving the dye into an emulsion, such as a method described in JP-A-50-80826, in which the dye is dissolved in an acid substantially free of water and the solution is added to the emulsion. Is preferably used. In addition, US Pat.
No. 3,342,605, No. 2,996,28
No. 7, No. 3,429,835 and the like. The above photosensitive dye may be uniformly dispersed in a silver halide emulsion before being coated on a suitable support,
Of course, it can be dispersed in any step of the preparation of the silver halide emulsion.

When two or more of the photosensitive dyes of the present invention are used in combination, the photosensitive dyes can be dispersed in the silver halide emulsion by the above-described methods either independently or in a premixed state. A dye having absorption in the visible region for the purpose of supersensitization, a dye having no spectral sensitization itself, or a substance which does not substantially absorb visible light together with the photosensitive dye of the present invention, A substance exhibiting a feeling may be contained in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176.
Volume 17643 (Issued December 1978) Page 23 IV J
Item, or JP-B-49-25500, 43-493
No. 3, JP-A-59-19032 and JP-A-59-19224.
No. 2, JP-A-3-15049, JP-A-62-1234
No. 54.

In the present invention, as the silver halide emulsion, Research Disclosure No. 30811
9 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described.

[Items] [Page RD308119] Iodine composition 993 IA section Manufacturing method 993 IA section and 994 E section crystal wall normal crystal 999 IA twin section 993 IA section Epitaxial 933 I- Section A Halogen composition uniform 993 IB Section Not uniform 993 IB Section Halogen conversion 994 IC Halogen substitution 994 IC Section Metal content 994 ID Monodispersion 990 IF Section Solvent addition 996 Item IF Latent image formation position Surface 995 I-G Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Item Emulsion mixed 995 I- Section J Desalting 995 II-A In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. Additives used in such a process are described in Research Disclosure No. 17643, no. 18716 and no. 3
08119 (hereinafter RD17643, RD18, respectively)
716 and RD308119). The places to be described are shown below.

[Item] [page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, 23-24 648-649 H, B, I , C, J section D section Supersensitizer 996 IV-AE, 23-24 648-649 J section Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known examples usable in the present invention. Are also described in Research Disclosure, supra. The relevant sections are described below.

[Item] [Page RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII- Item I 25-26 XIII-C Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) 1001 XXB Item Specific examples of DIR compounds that can be used in the present invention For example, JP-A-4-114 D-1 to D-34 of 53 Pat described are exemplified, the present invention can be preferably used those compounds. Specific examples of the diffusible DIR compound that can be used in the present invention include, in addition to the above, for example, US Pat. Nos. 4,234,678, 3,227,554, 3,647,291, and No. 3,958,993, No. 4,419,886,
No. 3,933,500, JP-A-57-56837.
No. 51-13239, U.S. Pat. No. 2,072,3.
No. 63, No. 2,070,266, Research Disclosure, December 21, 1981, No. 21228, and the like.

Various couplers can be used in the present invention, and specific examples thereof are described in the following Research Disclosure. The relevant sections are described below.

[Item] [RD308119] [RD17643] Yellow coupler 1001 VII-D Section VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G Section VIIG DIR coupler 1001 VII-F Section VIIF BAR coupler 1002 VII-F Other useful residue release 1001 VII-F Coupler A Alkali-soluble coupler 1001 VII-E The additive used in the present invention is described in RD308119XIV. It can be added by a conventional dispersion method.

In the present invention, the aforementioned RD17643
Page 28, RD18716 pages 647 to 648, and RD3
The support described in XIX of 08119 can be used. The light-sensitive material of the present invention includes the aforementioned RD3081
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19VII-K can be provided. The light-sensitive material of the present invention can have various layer structures such as a normal layer, a reverse layer, and a unit structure described in RD308119VII-K.

To develop the silver halide light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The
Theory of The Photograph
ic Process Forth Edition)
Pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society)
the American Chemical So
(See, for example, JP-A-4-15641 and JP-A-4-16841.) 1-phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4 such as aminophenol, N-methyl-p-aminophenol, and 2,4-diamiphenol
-Hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone, etc.) can be used alone or in combination.
Development can be carried out by the usual methods described in pages 7643, pages 28 to 29, RD18716, page 615 and RD308119XIX.

The details of the photothermographic material which is an embodiment of the photosensitive material of the present invention are described below.

The photothermographic material according to the present invention is described, for example, in US Pat. Nos. 3,152,904 and 3,457,07.
No. 5, and D.E. "Dry Silver Photo Material" by Morgan
Ophthalmic Material) and D.C. Morgan and B.A. "The Silver System Treated by Heat (Thermal)" by Shelly
ly Processed SilverSystem
s) "(Imaging Processes and Materials
d Materials) Neblette 8th edition,
Sturge, V.S. Wallworth (Wa
lworth), A.I. Shepp, 2nd page, 1969) and the like. Among them, the present invention is characterized in that an image is formed by thermally developing a photosensitive material at 80 to 140 ° C., and no fixing is performed.

The silver halide grains function as an optical sensor, and in order to suppress the cloudiness after image formation,
In order to obtain good image quality, it is preferable that the average particle size is small, the average particle size is 0.1 μm or less, more preferably 0.01 μm to 0.1 μm, and particularly 0.02 μm.
~ 0.08 µm is preferred. The term "grain size" as used herein refers to 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. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. It is more preferably 30 or less, particularly preferably 0.1%
The particles are at least 20% inclusive.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is high. It is preferable that this ratio is 50% or more, further 70% or more,
In particular, it is preferably at least 80%. Miller index [1
The ratio of the [00] plane is determined by utilizing the dependence of the adsorption of the photosensitive dye on the [111] plane and the [100] plane. Tan
i. Imaging Sci. , 29, 165 (1
985).

Another preferred form of silver halide is tabular grains. The term “tabular grain” as used herein means a thickness hμ in the vertical direction, where the square root of the projected area is a particle size rμm.
It means that the aspect ratio = r / h when m is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or more.
It is as follows. The particle size is preferably 0.1 μm or less, and more preferably 0.01 μm to 0.08 μm. These are described in U.S. Pat. Nos. 5,264,337, 5,314,798, and 5,320,958, and can easily obtain target tabular grains. When these tabular grains are used in the present invention, the sharpness of an image is further improved. There is no particular limitation on the halogen composition, and silver chloride, silver chlorobromide, silver chloroiodobromide,
Any of silver bromide, silver iodobromide and silver iodide may be used.

The photographic emulsion used in the present invention is a photographic emulsion. Gl
Chimie et Physique by Afkids
e Photographique (Paul Mon
tel, 1967); F. By Duffin
Photographic Emulsion Chem
istry (published by The Focal Press, 19
66); L. M by Zelikman et al
aking andCoating Photogra
phi Emulsion (The Focal P
Ress, published in 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 with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. 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 the organic acid silver and the halogen ion into silver halide, or may be prepared 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 preferably contains an ion or a complex ion of a metal belonging to Group 6 to Group 10 of the Periodic Table of the Elements, for the purpose of improving the illuminance failure and adjusting the improvement. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred. These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex ion is preferably a six-coordinate complex ion represented by the following general formula.

In the general formula [ML ₆ ] ^m , M is a transition metal selected from elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0,-, 2- or 3-.
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

Specific examples of the transition metal coordination complex ion are shown below.

[0063] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{2 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN )] ^2- 23: Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^{2 -} 27: [Ir (NS) Cl _5] ^2- also may with ions or complex ions one kind of these metals, the metal of the same kind of metal or different may be used alone or in combination.

The content of these metal ions or complex ions is generally in the range of 1 to 1 mol per mol of silver halide.
The amount is suitably from ^10-9 to ^1-10-2 mol, preferably 1 mol.
X 10 ^-8 to 1 X 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. In the addition, the compound may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added in the form of JP-A-63-29603 and JP-A-2-30.
No. 6236, No. 3-167545, No. 4-76534
No. 6,110-146, 5-273683 and the like, the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are mixed at the same time. To prepare silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of preparing silver halide. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance is sometimes 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.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method and a flocculation method, but in the present invention, they may or may not be desalted. Good.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. Preferred chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization, as is well known in the art. Sensitization can be used. Known compounds can be used as compounds preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method.
Compounds described in No. 8768 and the like can be used.
Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, and British Patent No. 618,0.
Compounds described in No. 61 or the like can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

In the present invention, the organic silver salt is a reducible silver source, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (10 to 30, preferably 15 to 25, And the nitrogen-containing heterocycle is 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. Examples of suitable silver salts are Research
h Disclosure Nos. 17029 and 29963
And salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (E.g., 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid; For example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5
-Dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes, for example, 3- (2-
Carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thioene and 3-carboxymethyl-
4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H
-Tetrazole, 3-amino-5-benzylthio-1,
Complexes or salts of silver with a nitrogen acid selected from 2,4-triazole and benzotriazole; saccharin, 5-
Silver salts such as chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, arachidic acid and / or stearic acid.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate and sodium arachidate, the above-mentioned soap and silver nitrate are added by a control double jet to prepare crystals of an organic silver salt. At that time, silver halide grains may be mixed.

In the present invention, the organic silver salt has an average particle size of 2
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.05 μm to 1.5 μm, particularly 0.05 μm
~ 1.0 µm is preferred. Monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.
It is.

In the present invention, the tabular grains of the organic silver salt preferably have at least 60% of the total organic silver.
In the present invention, the tabular grains mean those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between the average particle diameter and the thickness, that is, the following formula.

AR = Average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, the organic silver crystal is obtained by dispersing and pulverizing a binder, a surfactant and the like with a ball mill or the like. Can be Within this range, a photosensitive material having a high density and excellent image storability can be obtained.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably from 0.5 g to 2.2 g per m ² in terms of silver. With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is at most 50% by weight, preferably at most 25%, more preferably between 0.1% and 15%.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,593,863 and Research D
No. 17029 and 29996, and include the following: Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (eg, Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (E.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfhydroxamic acid) ;
Sulfonamidoanilines (for example, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (Eg, 1,2,3,4-tetrahydroquinoxaline); amide oximes; azines (eg, a combination of aliphatic carboxylic acid arylhydrazides and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and Hydrazines; hydroxamic acids; combinations of azines and sulfonamide phenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; Phenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (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).

[0074]

Embedded image

In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group having 1 to 5 carbon atoms (e.g., 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.

[0077]

Embedded image

[0078]

Embedded image

The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

Binders suitable for the photothermographic 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, (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), 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 (vinylacetal) s (eg, poly (vinylformal) and poly (vinylbutyral)), poly (ester) Kind, poly ( Urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). Although it may be hydrophilic or hydrophobic, in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after thermal development. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, and polyester are particularly preferably used.

Further, in order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer can be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, in order to increase the speed of thermal development, the amount of binder in the photosensitive layer is 1.5 to 10 g / m ^2.
It is preferred that More preferably, 1.7 to 8 g
/ M ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side. In order to prevent damage to the image after thermal development, it is preferable to provide a matting agent on the surface of the photosensitive material. It is preferable that the matting agent is contained in a weight ratio of 0.5 to 30% based on all binders on the photosensitive layer side.

When a non-photosensitive layer is provided on the opposite side of the photosensitive layer with the support interposed therebetween, it is preferable that at least one layer on the non-photosensitive layer side contains a matting agent, so that the slipperiness of the photosensitive material and the adhesion of fingerprints can be improved. For prevention, it is preferable to provide a matting agent on the surface of the photosensitive material, and the matting agent is used in a weight ratio of 0.5 to 4 with respect to all binders in the layer on the side opposite to the photosensitive layer side.
It is preferable to contain 0%.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starch described in U.S. Pat. No. 2,322,037, Belgian Patent No. 625,451 and British Patent No. 981,19
No. 8 and the like, and starch derivatives described in JP-B-44-3643.
No. 33, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like 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 preferably has a variation coefficient of the particle size distribution of 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, but is preferably used in order to achieve the object of the present invention. Is a constituent layer other than the photosensitive layer, and is more preferably the outermost layer as viewed from the support.

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 photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer, may be formed on the opposite side. A dye or a pigment may be included in the active layer.

As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range. Examples thereof include JP-A-59-6481 and JP-A-59-182.
No. 436, U.S. Pat.
594,312, EP-A-533,008,
No. 652,473, JP-A-2-216140, JP-A-4-348339, JP-A-7-191432, and JP-A-7-3
Compounds described in No. 01890 and the like are preferably used.

These non-photosensitive layers preferably contain the above-mentioned binder and matting agent, and may further contain a sliding agent such as a polysiloxane compound, wax and liquid paraffin.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer in order to adjust the gradation.

The photothermographic material of the present invention is for forming a photographic image by a heat development process, and comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, silver. It is preferable that the photothermographic material contains a color toning agent which suppresses the color tone of the present invention in a state of being usually dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but is exposed to high temperature (for example,
(0 ° C.). 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.

Examples of suitable toning agents used in the present invention are R
No. 17029, which includes the following:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms), and alkoxy. (E.g., those having one or more carbon atoms, preferably those having 1 to 4 carbon atoms). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole,
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole,
2-mercaptoquinoline, 8-mercaptopurine, 2,
3,5,6-tetrachloro-4-pyridinethiol,
-Hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole and the like,
The present invention is not limited to these.

The photothermographic material of the present invention may contain an antifoggant. Mercury compounds known from, for example, U.S. Pat. No. 3,589,903 as effective antifoggants are environmentally undesirable. For this reason, non-mercury antifoggants have been studied for a long time. Non-mercury antifoggants include, for example, U.S. Pat. Nos. 4,546,075 and 4,452,885 and JP-A-59-5723.
No. 4 is preferred.

Particularly preferred non-mercury antifoggants are disclosed in US Pat. Nos. 3,874,946 and 4,756,993.
No.9, -C (X ₁ )
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include JP-A-9-288328, paragraph [0030].
To [0036] are preferably used.

As another preferred example of the antifoggant, JP-A-9-90550, paragraph [006]
2] to [0063]. Further, other suitable antifoggants are disclosed in US Pat.
28,523 and British Patent Application No. 9221383.
No. 4, No. 9300147.7, No. 931179
No. 0.1.

The photothermographic materials of the present invention include, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414 and 4,740,455,
Nos. 4,741,966 and 4,751,175
No. 4,835,096. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item
17643 IV-A (p. 23, December 1978) and Item 1831X (p. 437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-806
The compounds described in No. 79 are preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and the other forming layers. In the photothermographic material of the present invention, for example, a surfactant, an antioxidant,
Stabilizers, plasticizers, ultraviolet absorbers, coating aids, and the like may be used. These additives and the other additives mentioned above are Research Disclosure Item 1
Compounds described in No. 7029 (pp. 9-15, June 1978) can be preferably used.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate,
Polyimide, nylon, cellulose triacetate, polyethylene naphthalate) are preferred. The thickness of the support is about 50 to 300 μm, preferably 7 to
0 to 180 μm. Further, a heat-treated plastic support can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is coated, at a temperature higher than the glass transition point of the support by 30 ° C. or more, preferably at a temperature higher by 35 ° C. or more, More preferably, the heating is performed at a temperature higher than 40 ° C. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

As the method of forming a film and the method of producing an undercoat according to the present invention, known methods can be used, but preferably, paragraphs [0030] to [0] of JP-A-9-50094 are used.
070].

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like.

In the present invention, US Pat.
The conductive compounds described in No. 773 columns 14 to 20 are preferably used.

[0109]

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 Photosensitive Material / Sample 101 >> The following composition was applied on a cellulose triacetate film support provided with an undercoat layer to prepare Sample 101 as a photosensitive material. In all the following examples, the addition amount of the silver halide photographic light-sensitive material particularly shows the number of grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver halide.

First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-1) 0.30 High boiling organic solvent (Oil-2) 0.17 Gelatin 1.59 Second layer: Intermediate layer High Boiling point organic solvent (Oil-2) 0.01 Gelatin 1.27 Third layer: infrared-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.70 Sensitizing dye (Dye-A) 5.0 × 10 ^-5 Magenta coupler (M-1) 0.20 High boiling point solvent (Oil-1) 0.34 Gelatin 0.90 4th layer: 1st protective layer Silver iodobromide emulsion (average particle size 0) 0.04 μm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0. 10 High boiling organic solvent (Oil-1) 0.44 High boiling organic solvent (Oil-3) 0.07 Gelatin 1.35 Fifth layer: Second protective layer Alkali-soluble matting agent (Average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size: 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.54 In addition to the above composition, compounds SU-1, SU-2, SU
-3, SU-4, viscosity modifier V-1, hardener H-1, H
-2, stabilizer ST-1, antifoggant AF-1, AF-
2. Two kinds of AF-3, weight average molecular weight: 10,000 and weight average molecular weight: 1,100,000, dye AI-
1, AI-2, AI-3, compounds FS-1, FS-2,
The preservative DI-1 was appropriately added to each layer.

[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube. Each emulsion was optimally subjected to gold, sulfur, and selenium sensitization.

Emulsion name Average AgI content Average grain size Crystal habit Diameter / thickness ratio (mol%) (μm) Silver iodobromide emulsion A 6.0 0.60 Twin plane plate 4.0 Silver iodobromide emulsion B 8 0.0 0.90 Twin plane plate 3.0 << Preparation of Samples 102 to 108 >> The photosensitive dye Dye-A (comparative sensitizing dye) used for the third layer of Sample 101 was equimolarly increased in Table 1. Sample 10 except that the dye was replaced.
Samples 102 to 108 were produced in exactly the same manner as in 1.

<Evaluation of relative sensitivity and fog of color negative>
Next, each of the obtained coating samples 101 to 108 was converted into 135
The test piece was cut to the standard and left under the following two conditions to prepare a test sample for substitution of storage stability.

Condition A: Reference sample left for 4 days at 23 ° C. and 55% RH Condition B: Storage test sample left for 4 days at 40 ° C. and 80% RH Each of the obtained samples was a Kodak Wratten filter 89B. Was used to perform 1/100 second infrared exposure, color development treatment (CNK-4 manufactured by Konica), and drying to obtain a sample for evaluation. Each of the obtained evaluation samples was evaluated for relative sensitivity and fog as described below.

<< Evaluation Method >><< Fog Density >> The fog density is shown in Table 1 as a green light transmission density value obtained using a Konica PD transmission densitometer.

<< Relative Sensitivity >> The relative sensitivity is defined as fog density + 0.
It is a relative value of the reciprocal of the exposure amount that gives a density of 15 and is shown in Table 1 with a value where the sensitivity of the sample 101 is 100.

<< Evaluation of stagnation property and storage property >> The stagnation property was determined by aging a coating solution at a temperature of 40 ° C. for 30 minutes. The sample applied after being aged for 8 hours, the sensitivity of the sample stored under the storage conditions A as SCA,
The value of ΔSp (SiA / SCA) was used as a measure of sensitivity fluctuation due to stagnation after preparation of the coating solution.

Further, the sensitivity of the sample stored under the above-mentioned storage condition B was changed to S
CB and the sensitivity of the sample stored under the storage condition A was SC
As A, the value of ΔSs (SCA / SCB) was used as a measure of the sensitivity fluctuation of the storage property. Further, the fog of the sample stored under the storage condition A is FCA, and the fog of the sample stored under the storage condition B is FCB, and ΔFs (F
CB-FCA) was determined and used as a measure of the fog variation of the shelf life.

As the values of ΔSp and ΔSs approach 1,
The smaller the ΔFs value, the better the production stability (stagnation) and the storage stability over time.

Table 1 shows the above results.

[0128]

[Table 1]

[0129]

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As is clear from Table 1, the silver halide photographic light-sensitive material obtained according to the present invention is excellent in both fog and relative sensitivity, has little fluctuation in sensitivity due to stagnation of the coating solution, and preserves raw film with time. The properties were good.

Example 2 [Preparation of Subbed Photographic Support] <Preparation of PET Subbed Photographic Support> A commercially available biaxially stretched heat-fixed blue-colored PET film having a thickness of 175 μm was formed on both sides. 8w / m ² · min corona discharge treatment
On one surface, the following undercoating coating solution a-1 was dried to a thickness of 0.8 μm.
And then dried to form a subbing layer A-1. On the other side, the following antistatic coating subbing coating solution b-1 is applied to a dry film thickness of 0.8 μm and dried. In this way, an antistatic subbing layer B-1 was obtained.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) Copolymer latex liquid of 2-hydroxyethyl acrylate (25% by weight) (Solid content 30%) 270 g (C-1) 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water << Subtraction coating solution b-1 >> Butyl acrylate (40 weight %) Styrene (20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0. 8g Finished to 1 liter with water Then, on the upper surface of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 w / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating Solution a-2 for Undercoating >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 liter with water << Lower coating solution for upper layer b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0 0.5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0134]

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[0135]

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(Heat Treatment of Support) In the above-described undercoat drying step of the support, the support was heated at 140 ° C.
Thereafter, it was gradually cooled.

(Preparation of silver halide emulsion) 900 ml of water
Inert gelatin 7.5g and potassium bromide 10m
g was dissolved and the temperature was adjusted to 35 ° C. and the pH to 3.0.
370 ml of an aqueous solution containing 74 g of silver nitrate, 370 ml of an aqueous solution containing potassium bromide and potassium iodide (equimolar to the above silver nitrate) in a molar ratio of (98/2) and K ₂ [Ir (N
O) Cl ₅ ] salt was added in an amount of 1 × 10 ^-6 mole per silver mole and rhodium chloride salt in an amount of 1 × 10 ^-6 mole per silver mole, pA
After the addition by the controlled double jet method while maintaining the pH at 7.7, reduction sensitization was performed at pH 8.7 and pAg 6.5. Thereafter, 4-hydroxy-6-methyl-1,
Add 3,3a, 7-tetrazaindene and add NaOH to p.
By adjusting H to 5, cubic silver iodobromide grains having an average grain size of 0.06 μm, a coefficient of variation of 8%, and a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting, and then 0.1 g of phenoxyethanol was added.
H5.9 and pAg7.5 were adjusted to obtain a silver halide emulsion.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C.

Next, 98 ml of a 1.5 M aqueous sodium hydroxide solution was added while stirring at a high speed. Next, concentrated nitric acid was added.
After adding 93 ml, the mixture was cooled to 55 ° C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide Emulsion) 15.1 g of the above silver halide emulsion was added to the above-mentioned sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. 147m of silver nitrate solution
was added over 7 minutes, and the mixture was further stirred for 20 minutes, and the water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, the water was removed, washed with water six times and water was removed, and dried.

(Preparation of Photosensitive Emulsion) A polyvinyl butyral (average molecular weight: 300
544 g of 0) methyl ethyl ketone solution (17 wt%)
And 107 g of toluene were gradually added and mixed.
It was dispersed at 80 kgf / cm ² .

Coating on the back side: A coating solution for the back layer having the following composition was applied to the above support by an extrusion coater to form an upper layer B
-2 was applied on the side to which it was applied so as to have a wet film thickness of 30 μm, and dried at 60 ° C. for 3 minutes.

Back layer coating solution: Cellulose cellulose acetate butyrate (10% methyl ethyl ketone solution) 15 ml / m ² dye-B 7 mg / m ² dye-C 7 mg / m ² Matting agent: monodispersity 15% Average particle size 8 μm single Dispersed silica 30 mg / m ² C ₉ F ₁₉ —C ₆ H ₄ —SO ₃ Na 10 mg / m ²

[0144]

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Coating on photosensitive layer side: Subbing layer A of the above support
-2 was coated with a photosensitive layer coating solution having the following composition and a protective layer coating solution thereon by an extrusion coater at a speed of 20 m / min. At that time, the coated silver amount was 2.4 g / m ^2.
It was adjusted so as to be applied. Thereafter, drying was performed at 55 ° C. for 15 minutes.

Photosensitive layer coating solution: Preform emulsion 240 g Photosensitive dye (described in Table 2) (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% 1.7 ml Antifoggant-2 (10% methanol solution) 1.2 ml 2-Chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml Tri Bromomethylsulfoquinoline (5% methanol solution) 17 ml Developer A-4 (20% methanol solution) 29.5 ml Phthalazine 0.6 g 4-methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g

[0147]

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[0148] surface protective layer coating solution: acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² methanol 7 ml / m ² phthalazine 250 mg / m ² Matting agent: monodisperse degree of 10% average particle size 4 μm monodispersed silica 70 mg / m ² CH ₂ ＨH—SO ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —SO ₂ —CH = CH ₂ 35 mg / m ² C ₉ H ₁₉ —C ₆ H ₄ —SO ₃ Na 10 mg / m ² << Exposure and development treatment >> The photothermographic material prepared above was exposed with an imager having a semiconductor laser of 810 nm. Thereafter, heat development was performed at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

<< Evaluation of Fog Density >> The optical density of the unexposed portion of the developed sample was measured. The smaller the value, the better.

<< Relative Sensitivity >> The relative sensitivity is defined as fog density + 1.
The relative value of the reciprocal of the exposure amount giving a density of 0
Table 1 shows the values with the sensitivity of -1 as 100.

<< Evaluation of Sensitivity and Fog Density of Forced Degradation Sample >> The photothermographic material prepared above was divided into two parts, and one of them was put into a thermo machine at 40 ° C. and 50% relative humidity for 5 days.
The fog density and sensitivity were measured.

Table 2 shows the results of the evaluation.

[0153]

[Table 2]

[0154]

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As is evident from Table 2, the heat-developable silver halide photographic light-sensitive material obtained according to the present invention is excellent in both fog and relative sensitivity, and has little fluctuation in sensitivity and fog after forced deterioration treatment. The storage stability of the film over time was good.

[0156]

According to the present invention, a silver halide light-sensitive material having an infrared-sensitive silver halide emulsion layer having excellent stability, high sensitivity and low fog can be provided.

Continued on the front page F term (reference) 2H023 CA07 2H123 AB00 AB03 AB18 AB23 AB28 BB00 BB23 CB00 CB03 4H056 CA01 CA04 CA05 CB01 CC08 CE03 CE06 DD04 DD19 DD23 DD30 FA05

Claims (5)

[Claims] 1. A silver halide emulsion comprising at least one compound represented by the following general formula [1] or [2]. Embedded image (In the general formulas [1] and [2], Y ₁ , Y ₂ and Y ₁₁
Is an oxygen atom, a sulfur atom, a selenium atom or -C
H represents a CH- group, and L _{1 to} L ₉ and L _{11 to} L ₁₅ each represent a methine group. R ₁ , R ₂ , R ₁₁ and R ₁₂ each represent an aliphatic group, and R ₃ , R ₄ , R ₁₃ and R ₁₄ each represent an alkenyl group, a cyclic alkyl group or a heterocyclic group. W ₁ , W ₂ , W
₃ , W ₄ , W ₁₁ , W ₁₂ , W ₁₃ and W ₁₄ are each a hydrogen atom,
Substituents or W ₁ and W ₂ , W ₃ and W ₄ , W ₁₁ and W ₁₂ , W ₁₃
And W ₁₄ represent a group of nonmetallic atoms necessary to form a fused ring. X ₁ and X ₁₁ each represent an ion necessary to cancel the intramolecular charge, and k1 and k11 each represent the number of ions required to cancel the intramolecular charge. m1 represents 0 or 1, and n1, n11, and n12 represent 0, 1, or 2, respectively. However, n11 and n12 do not become 0 at the same time. ) 2. A silver halide emulsion comprising at least one compound represented by the following general formula [3] or [4]. Embedded image (In the general formulas [3] and [4], Y ₂₁ , Y ₂₂ and Y
₃₁ is an oxygen atom, a sulfur atom, a selenium atom or-
L represents a CH = CH- group, and L _{21 to} L ₂₉ and L _{31 to} L ₃₅ each represent a methine group. R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ each represent an aliphatic group. R ₂₃ , R ₂₄ , R ₃₃ and R ₃₄ each represent a group selected from an ethenyl group, a cyclopropyl group and a cyclobutyl group, and W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ , W ₃₁ ,
Each W _32, W ₃₃ and W ₃₄ is a hydrogen atom, a substituent, or W ₂₁ and W _22, W ₂₃ and W _24, W ₃₁ and W _32, fused bonded to between W ₃₃ and W ₃₄ Represents the group of non-metallic atoms necessary to form. X ₂₁ and X ₃₁ each represent an ion required to cancel an intramolecular charge, and k21 and k31 each represent the number of ions required to cancel an intramolecular charge. m21 represents 0 or 1, and n21, n31 and n32 each represent
Represents 0, 1 or 2. However, n31 and n32 are simultaneously 0.
Does not. ) 3. A silver halide light-sensitive material having at least one hydrophilic non-light-sensitive layer and a light-sensitive silver halide emulsion layer on a support, wherein at least one of the light-sensitive silver halide emulsion layers is provided. 3. A silver halide photosensitive material comprising the silver halide emulsion according to claim 1 in one layer. 4. A photothermographic material comprising an organic silver salt, photosensitive silver halide particles, a reducing agent, and at least one of the compounds represented by the general formulas [1] to [4]. . 5. A compound represented by the general formula [3] or [4].