JPH10147727A - Silver halide photosensitive material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photosensitive material improved in long-term stability by adding water-miscible solution containing a specified compound and a specified colorant to a silver halide emulsion. SOLUTION: 0.0000001-10g/l of a compound represented by formula I (wherein R<1> to R<5> are each H, an alkyl or an aryl, provided at least two of them are carboxylakyls or alkylesters thereof, (h) and (i) are each 2 or 3; (j) is 0-2; and (k) is 0 or 1) and a red sensitizing colorant represented by formula II or III [wherein Z1 to Z3 are each an atomic group necessary to form a five- or six- membered nitrogenous heterocyclic ring; D and D' are each an atomic group necessary to form an (a) cyclic acid e nucleus; R1 to R3 are each an alkl; L1 to L21 are each a (substituted) methine; n1 to n4 and (j) are each 0 or 1; M1 and M2 are each a counter ion neutralizing the charge; m1 and m2 are each a number necessary to neutralize the charge of the molecule and equal to or greater than 0; and Z1 to Z3 are each a benzothiazole nucleus or the like] are dissolved in water or a water-miscible solution comprising water and a water- miscible organic solvent. This solution in such an amount that the amount of the compound represented by formula I is 1wt.% or below based on the silver atoms, is added to a silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an infrared-sensitive silver halide photographic material and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, as semiconductor lasers emitting infrared light have become widespread as light sources, demand for infrared-sensitive silver halide photographic materials has been increasing. It has long been known that a sensitizing dye that absorbs red or infrared light is added to a silver halide emulsion and subjected to spectral sensitization in the infrared region, whereby a photographic photosensitive material that feels infrared light can be obtained. However, infrared sensitizing dyes or infrared dyes generally used to absorb unnecessary light such as halation are unstable. However, there is a problem that it is difficult to produce a photosensitive material of stable quality due to deterioration over time, and that the performance of an infrared-sensitive photographic photosensitive material produced using the same is liable to change during storage. In order to solve this problem, for example, the Photographic Society of Japan, Vol. 57, published in 1994,
Attempts have been made to improve the structure of infrared sensitizing dyes as shown in the article published on page 304, but such methods requiring specific structural modification are not necessarily common to dyes having a wide range of structures. It was not applicable. Therefore, a technique for stabilizing a versatile infrared dye has been demanded. on the other hand,
For example, US Pat. No. 2,666,700, 3458316
, British Patents 1221137 and 1221138, JP-B-49-26120, JP-A-54-103017.
JP-A-55-156935, JP-A-57-196
No. 228, and a silver halide photographic light-sensitive material containing a masking agent for metal ions such as polyaminocarboxylic acid for the purpose of sensitization, emulsion stabilization, spot prevention, dissolution of silver halide and the like. However, there is no description about an infrared-sensitive silver halide photographic material, and a combination with an infrared sensitizing dye is disclosed in JP-A-63-15 / 1988.
No. 9840 also described that a considerably large amount of addition was required to exhibit these effects. Also,
Use of a metal ion masking agent such as polyaminocarboxylic acid for stabilizing an infrared dye, or use of a dye composition in which a metal ion masking agent such as polyaminocarboxylic acid is mixed with an infrared dye, There was no known method for producing a silver halide photographic light-sensitive material.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an infrared-sensitive silver halide photographic material having excellent aging stability. Another object of the present invention is to provide an infrared-sensitive silver halide photographic material. Another object of the present invention is to provide a production method excellent in production stability.

[0004]

The object of the present invention has been attained by the following means. (1) A silver halide photographic material comprising a compound represented by the following general formula (I) in an amount of less than 1% by weight of silver. General formula (I)

[0005]

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In the formula, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ represent a hydrogen atom, an alkyl group or an aryl group, and at least two of them represent a carboxyalkyl group or an alkyl ester thereof; i is independently 2 or 3
And j represents 0, 1, or 2, and k represents 0 or 1.
Represents (2) The silver halide photographic material as described in (1) above, which has a spectral sensitivity maximum at a wavelength longer than 700 nm. (3) A method for producing a silver halide photographic material, comprising adding a water-miscible solution containing both the compound represented by formula (I) and a dye to a silver halide emulsion. (4) A dye composition comprising a water-miscible solution containing both the compound represented by formula (I) and an infrared dye.

[0007]

The stability over time is improved by the infrared-sensitive silver halide photographic light-sensitive material of the present invention. The production stability is improved by the production method of the present invention.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (I) will be described in detail. R ¹ , R ² , R ³ , R ⁴ , R ⁵
The alkyl group represented by is preferably an alkyl group having 1 to 4 carbon atoms and may have a substituent. Preferred examples of the substituent include a hydroxy group, a carboxy group, and an alkyl group having 1 to 6 carbon atoms. An alkoxy group, an acyl group having 2 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, particularly preferably a hydroxy group or a carboxy group. The most preferred group as R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a carboxymethyl group. R ¹ ,
As the aryl group represented by R ² , R ³ , R ⁴ , and R ⁵ , a phenyl group or a group having 6 to 10 carbon atoms is preferable.
The preferred phenyl group is a halogen atom, a cyano group, a hydroxy group, a carboxy group, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms. 8 is an alkoxycarbonyl group. h and i are preferably 2, j is preferably 0 or 1, and k is preferably 1.

Next, specific examples of the compound represented by formula (I) of the present invention will be given, but the scope of the present invention is not limited only to these.

[0010]

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[0011]

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Many of these compounds are commercially available,
For the synthesis method, see, for example, H. By Mueller, A
rchiev der Pharmazie, 307
Vol. 5, No. 336, p. 336 (issued in 1974) can be referred to.

The compounds represented by the general formula (I) of the present invention may be used alone or in combination of two or more. The amount added to the silver halide emulsion is determined by the amount of silver of the silver halide in the emulsion. Preferably less than 1 weight percent, particularly preferably 0.000
001 percent to 0.01 percent. Although a stabilizing effect is exhibited even if the addition amount is larger than this, it is not necessarily preferable because a sensitizing or desensitizing effect is remarkably exhibited depending on the type of the emulsion.

The infrared dye used in the present invention has a component in the infrared region.
Spectral sensitizing dye for imparting light sensitivity, absorbing unnecessary light
Antihalation dyes, or
It is an anti-dye dye. Cyani as an infrared sensitizing dye
And merocyanine dyes are preferred.
Are preferred. Infrared dyes include cyanine and melocene
Anine-based and oxonol-based dyes are preferred, and cyanine
Systems or oxonol systems are particularly preferred. These alone
Or two or more of them may be used in combination. These sensitizing dyes
In an amount of 10 per mole of silver of the silver halide emulsion.^-8Mo
Or 10^-3Mole, preferably 10^-8Mole to 10
^-FourIs a mole. The amount of infrared dye added is 10 ^-8Or 1 mo
, Preferably 10^-6Or 10^-1Is a mole. Infrared increase
Examples of the sensitizing dye include the following general formula (II) or (II)
The compound represented by I) is mentioned. General formula (II)

[0015]

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Formula (III)

[0017]

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Wherein Z ₁ , Z ₂ and Z ₃ are each 5
Alternatively, it represents an atomic group necessary for forming a 6-membered nitrogen-containing heterocyclic ring. D and D 'each represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus. R ₁ , R ₂ and R ₃ each represent an alkyl group. L ₁ , L ₂ ,
L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , L ₉ , L ₁₀ , L
_{11, L 12, L 13,} L 14, L 15, L 16, L 17, L 18,
L ₁₉ , L ₂₀ and L ₂₁ each represent a methine group or a substituted methine group. Further, a ring may be formed with another methine group, or a ring may be formed with an auxochrome. n ₁ , n
₂ , n ₃ and n ₄ represent 0 or 1. j represents 0 or 1. M ₁ and M ₂ represent a charge neutralizing counter ion, and m ₁ and m ₂ are zero or more necessary to neutralize the charge in the molecule.

The general formulas (II) and (III) will be described below in more detail. R ₁ , R ₂ and R ₃ are preferably an unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl,
Decyl, dodecyl, octadecyl) or a substituted alkyl group {eg, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, fluorine, chlorine, bromine),
A hydroxy group, an optionally substituted alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an optionally substituted alkoxy group having 8 or less carbon atoms (eg, methoxy, Ethoxy, benzyloxy, phenethyloxy), a monocyclic optionally substituted aryloxy group having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy), an optionally substituted acyloxy group having 3 or less carbon atoms (eg, Acetyloxy, propionyloxy), an optionally substituted acyl group having 8 or less carbon atoms (eg, acetyl, propionyl, benzoyl,
Mesyl), an optionally substituted carbamoyl group having 8 or less carbon atoms (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), and an optionally substituted sulfamoyl group having 8 or less carbon atoms (eg, , Sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl) or an optionally substituted aryl group having 10 or less carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α -Naphthyl), and an alkyl group 以下 having 18 or less carbon atoms.

Preferably, an unsubstituted alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group,
-Pentyl group, n-hexyl group), carboxyalkyl group (eg, 2-carboxyethyl group, carboxymethyl group), sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3 −
Sulfobutyl group).

(M ₁ ) _m1 and (M ₂ ) _m2 are used in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye. Is included. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion can be specifically either an inorganic or organic anion, such as a halogen anion (eg, fluorine). Ion, chloride ion,
Bromide ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-
Chlorobenzenesulfonic acid ion), aryldisulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6
-Naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonic acid ion. Can be Preferably, they are an ammonium ion, an iodine ion, and a p-toluenesulfonic acid ion.

The nucleus formed by Z ₁ , Z ₂ and Z ₃ includes a thiazole nucleus and a thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-dimethylthiazole). Diphenylthiazole), benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-
Nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzo Thiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5
-Chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 5-phenylbenzothiazole), naphthothiazole nucleus ( For example, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [ 2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2
3-d] thiazole)}, thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (eg, oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole) , 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-
Methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5- Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole,
5,6-dimethylbenzoxazole, 4,6-dimethylbenzothiazole, 5-ethoxybenzoxazole), naphthooxazole nucleus (for example, naphtho [2,1
-D] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-d] oxazole)}, an oxazoline nucleus (for example, 4,4-dimethyloxazoline) ), Selenazole nucleus selenazole nucleus (for example, 4-methyl selenazole, 4-nitro selenazole, 4-phenyl selenazole), benzo selenazole nucleus (for example, benzo selenazole, 5-chlorobenzo selenazole, 5-nitro Benzoselenazole, 5-methoxybenzoselenazole,
5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d]) Selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (e.g., selenazoline, 4-methylselenazoline), tellurazole nucleus {terrazole nucleus (e.g.,
Tellurazole, 4-methyltellurazole, 4-phenyltellurazole), benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-
Methylbenzotellurazole, 5,6-dimethylbenzotellurazole, 6-methoxybenzotellurazole), naphthotellurazole nucleus (for example, naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole) , A terrazoline nucleus (eg, tellurazoline, 4-methyltellurazoline), a 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5- Cyanoindolenine, 3,3-dimethyl-6-nitroindolenine,
3,3-dimethyl-5-nitroindolenine, 3,3-
Dimethyl-5-methoxyindolenine, 3,3,5-methylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus ｛indazole nucleus (for example, 1-alkylimidazole, 1-alkyl-4- Phenylimidazole, 1-arylimidazole), benzimidazole nucleus (for example, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxy) Benzimidazole,
1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-
Alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5
-Cyanobenzimidazole), naphthoimidazole nucleus (for example, alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), and the above-mentioned alkyl group having 1 to 8 carbon atoms For example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl, and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl)
Is preferred. Particularly preferred are a methyl group and an ethyl group. The aforementioned aryl groups represent phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) substituted phenyl. ｝, Pyridine nucleus (for example, 2-pyridine, 4
-Pyridine, 5-methyl-2-pyridine, 3-methyl-
4-pyridine), quinoline nucleus {2-quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-
Nitro-2-quinoline, 8-fluoro-2-quinoline,
6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline), 4-quinoline nucleus (for example, 4-quinoline, 6-ethoxy-4-quinoline, 6-phenyl-4-quinoline) 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4
-Quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (for example, 6-
Nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (for example, 1,3-
Examples thereof include diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

The nucleus formed by Z ₁ , Z ₂ and Z ₃ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus or a 4-quinoline nucleus. is there.

D and D 'represent a group of atoms necessary for forming an acidic nucleus, but can take the form of an acidic nucleus of any general merocyanine dye. D in the preferred form
Is a thiocarbonyl group or a carbonyl group, and D represents a group of remaining atoms necessary for forming an acidic nucleus.

D and D 'can together form a 5- or 6-membered heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Preferably, the next core is completed.

2-pyrazolin-5-one, pyrazolidin-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one ,
2-thiooxazolidin-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, Isorhodanine, indane-1,3-dione, thiophene-3-
On, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, indazolin-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7- Dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbi Tool acid, 2-thiobarbituric acid, chroman-
The core of 2,4-dione, indazolin-2-one, or pyrido [1,2-a] pyrimidin-1,3-dione.

More preferably, 3-alkyl rhodanine, 3-alkyl-2-thiooxazolidine-2,4-
Dione, 3-alkyl-2-thiohydantoin.

The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl,
Hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (eg, aralkyl groups (eg, benzyl, 2-phenylethyl), hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl groups (eg, , 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), a sulfoalkyl group (for example, 2- Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-
Sulfobutyl, 2- [3-sulfopropoxy] ethyl,
2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine- 2-one-1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl), allyl group, aryl group (for example, phenyl, 2-naphthyl) ), Substituted aryl groups (eg, 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl), heterocyclic groups (eg, 2
-Pyridyl, 2-thiazolyl) is preferred.

More preferably, an unsubstituted alkyl group (eg, methyl, ethyl, n-propyl, n-butyl, n-butyl)
-Pentyl, n-hexyl), carboxyalkyl group (eg, carboxymethyl, 2-carboxyethyl), sulfoalkyl group (eg, 2-sulfoethyl)
It is.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ and L ₂₁ each represent a methine group or a substituted methine group such as a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group,
-Carboxyethyl group), substituted or unsubstituted aryl group (eg, phenyl group, o-carboxyphenyl group), heterocyclic group (eg, barbituric acid), halogen atom (eg, chlorine atom, bromine atom), alkoxy Group (eg, methoxy group, ethoxy group), amino group (eg, N, N-diphenylamino group, N-methyl-N-phenylamino group, N-methylpiperazino group), alkylthio group (eg, methylthio group, ethylthio group) ) And the like, represents｝, may form a ring with another methine group, or may form a ring with an auxochrome. It is preferable that any one of L ₂ and L ₄ and L ₃ and L ₅ form a ring with each other. Also, L
It is preferable that one of the set of L ₁₂ and L ₁₄ , L ₁₃ and L ₁₅ , and L ₁₄ and L ₁₆ forms a ring with each other. L ₂ and L _4, then mention particularly preferred ring structure as a ring L ₁₂ and L _14, L ₁₄ and L ₁₆ are formed.

[0031]

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Particularly preferred ring structures for the ring formed by L ₃ and L ₅ and L ₁₃ and L ₁₅ are as follows.

[0033]

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L ₄ and L ₁₄ are preferably an unsubstituted methine group, an unsubstituted alkyl group (eg, methyl), an alkoxy group (eg, methoxy), an amino group (eg, N, N-diphenylamino), a halogen A methine group substituted with an atom (eg chlorine) or D and D ′
A methine group substituted by an acidic nucleus as represented by The other L is preferably an unsubstituted methine group.

Examples of other preferable infrared sensitizing dyes include JP-A-59-192242 and JP-A-60-80841.
62-299838, 64-86136, JP-A-2
-35444, 2-134630, 2-132243
3, 2-196237, 2-225476, 2-
264937, 3-13838, 3-13864
2, 3-244667, 3-282449, 4-
104139, 4-255840, 4-28024
6, 4-335342, 4-338746, 4-
362932, 5-45774, 5-45775,
5-72659, 5-72660, 5-7266
1, 5-72663, 5-72662, 5-45
828, 5-241265, 5-249599, 5-265120, 5-297500, 5-297
501, 5-313285, 5-313289, 6-102614, 6-95282, 6-2224
92, 6-202263, 6-230506, 6
-250323, 6-265120, 6-3178
68, 6-301141, 7-333778, 8
-95187, European Patents 420011A and 44346
6A, 566832A2, 595088A1, U.S. Pat. No. 5,223,389, Soviet Union Patent 1549027
A1, 1730932A1, 1780427A1,
Patent No. 1010841A1, Russian Patent 2041483C1
And sensitizing dyes described in (1). Examples of infrared dyes include JP-A-62-123454 and JP-A-2-123454.
282244, 3-9346, 3-26765, 3-138640, 3-212542, 3-226
736, JP-A-4-13654 and JP-A-4-190343,
JP-A-5-313305, JP-A-5-323500, JP-A-5-313500
323501, JP-A-6-43583, U.S. Pat.
09,989, 5,380,635, European Patent 377
961B, 430244A, 568267A, "Coloring Materials", Vol. 61, No. 4, pp. 215-226 (published in 1988), "Chemical and Industrial", May 1986, 43-5.
Dyes described on page 3 can be mentioned.

In the present invention, the solvent used for preparing a solution in which the compound represented by the general formula (I) and the infrared sensitizing dye are dissolved is water or an organic solvent miscible with water. May be used in combination. Among the water-miscible organic solvents, those having a vapor pressure equal to or higher than that of water are particularly preferable because they are easy to dry after coating the photographic emulsion. Preferred examples of the water-miscible organic solvent include methanol, ethanol,
Alcohols such as isopropyl alcohol, 2,2,3,3-tetrafluoro-1-propanol, benzyl alcohol, propylene glycol and ethylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; N, N-dimethylformamide; Amides such as -methylpyrrolidone, sulfoxides such as dimethylsulfoxide, phosphates such as trimethylphosphoric acid, and the like.
Particularly preferred are methanol, ethanol, isopropyl alcohol, a mixture of at least two of these, or a mixture of at least one of these with water.

The concentration of the infrared sensitizing dye solution used in the present invention can be arbitrarily selected as long as the infrared sensitizing dye or the compound of the formula (I) is completely dissolved. 0.000 solute weight per liter
0001 g to 10 g, particularly preferably 0.0000
1 g to 1 g.

The time for adding the infrared sensitizing dye solution of the present invention to the silver halide emulsion can be selected at any time from the start of the formation of silver halide grains to the application of the silver halide emulsion. .

The dye composition of the present invention may contain compounds of the general formula (I), dyes, and other compounds in solvents, such as acids (eg, acetic acid, paratoluenesulfonic acid), and the like. Bases (for example, triethylamine), surfactants and the like can be mentioned.

The silver halide emulsion which can be used in the present invention is:
It may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. The silver halide grains may have regular crystals such as cubic, octahedral, tetradecahedral, and rhombodecahedral, or irregular crystals such as spherical, plate-like, etc. It may have a shape or a compound of these crystal forms. It may consist of a mixture of particles of different crystal forms.
As the plate-like particles, the thickness is 0.5 microns or less,
50% (area) of grains having an average aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 5 or more, preferably 0.3 μm or less and an equivalent circle diameter of 0.6 μm or more. Tabular grains occupying the above are preferred. The silver halide grains may have different phases between the inside and the surface layer or may consist of a uniform phase. Further, the grains may be such that a latent image is mainly formed on the surface (for example, a negative emulsion) or may be the grains that are mainly formed inside the grains (for example, an internal latent image type emulsion). Core / shell types are also used. Hereinafter, preferred silver halide emulsions in the invention will be described in detail. The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or an irregular shape such as spherical or tabular.
lar) Those having a crystal form or those having a complex form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. The silver chlorobromide emulsion used in the present invention is described in Chimie et al. By P. Glafkides.
Phisique Photographique (Paul Montel, 1967
Year), Photographic Emulsion Chemistry by GFDuffin
(Focal Press, 1966), VLZelikman et al
By Makingand Coating Photographic Emulsion (Focal P
ress, published in 1964) and the like. That is, acid method, neutral method,
Any of ammonia and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt includes a one-side mixing method,
Any method such as a simultaneous mixing method and a combination thereof may be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. In particular,
Group VIII elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide. The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization. As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-215272.
Those described in the lower right column on page 8 to the upper right column on page 22 are preferably used. To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. Specific examples of these compounds are described in the above-mentioned JP-A-62-21.
Those described on page 39 to page 72 of JP-A-5272 are preferably used.

The emulsion used in the present invention is preferably a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface. When a semiconductor laser is used as a light source for digital exposure in the present invention, it is necessary to efficiently spectrally sensitize the infrared region. In the case of infrared sensitization, when sensitization by the M band of the sensitizing dye is used, the spectral sensitivity distribution is generally broader than that by the J band. For this reason, it is preferable to correct the spectral sensitivity distribution by providing a coloring layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer. This colored layer is effective for preventing color mixing by a filter effect. To incorporate the spectral sensitizing dyes into the silver halide emulsion, they may be dispersed directly in the emulsion, or may be dispersed in water, methanol, ethanol, propanol, methylcellosolve, 2,2,3,3- It may be dissolved in a solvent such as tetrafluoropropanol alone or in a mixed solvent and added to the emulsion. In particular, it is preferable to add the dye composition of the present invention. In addition, Shoko 4
No. 4,23,389, JP-B-44-27555, JP-B-57-2289, and the like.
As described in U.S. Pat. No. 4,060,025, an aqueous solution or colloidal dispersion in the presence of a surfactant may be added to the emulsion. After dissolving in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. JP-A-53-102733, JP-A-58-105
As described in No. 141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The timing of addition to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful. In other words, before the silver halide emulsion is formed, during the grain formation, immediately after the grain formation, before entering the washing step, before the chemical sensitization, during the chemical sensitization, and immediately after the chemical sensitization until the emulsion is cooled and solidified, during the preparation of the coating solution. , You can choose from. Most commonly, it is performed after completion of chemical sensitization and before coating, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, it is added simultaneously with a chemical sensitizer and distributed. It is also possible to perform sensitization simultaneously with chemical sensitization as described in JP-A-58-1.
It can be carried out prior to chemical sensitization as described in No. 13928, or it can be added before completion of precipitation of silver halide grains to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, spectral sensitizing dyes can be added separately, i.e., some added prior to chemical sensitization and the remainder added after chemical sensitization. It is possible at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion or before the chemical sensitization. The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 × 10 5 per mol of silver halide.
The range of ^-6 mol to 1.0.times.10.sup.- ² mol is preferable. More preferably, the range is 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³ mol. In the red or infrared sensitization of the present invention, the M-band sensitization is preferably carried out by using the compounds described in JP-A-2-157494, page 13, right lower column, line 3 to page 22, right lower column, bottom three lines. Is effective for supersensitization.

The light-sensitive material according to the present invention is coated with a hydrophilic colloid layer in order to improve the sharpness of an image and the like, as described in EP-A-0,337,490A2, Nos. 27-
A dye capable of being decolorized by treatment (among which is an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, or a water-resistant resin for the support is used. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with dihydric or tetravalent alcohols (for example, trimethylolethane) in the layer.
It is preferable to include them.

In the light-sensitive material of the present invention, colloidal silver and dyes are used for preventing irradiation and halation, in particular, for separating the spectral sensitivity distribution of each light-sensitive layer and ensuring safety against safelight.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in EP 0,277,589 A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred. Further, the light-sensitive material according to the present invention may contain an antifungal agent as described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add. Further, as the support used in the light-sensitive material according to the present invention, a white polyester-based support for a display or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used. May be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. The exposed light-sensitive material can be subjected to conventional black-and-white or color development processing. In the case of a color light-sensitive material, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.
Examples of the cyan coupler include a diphenylimidazole-based cyan coupler described in JP-A-2-33144, and a 3-hydroxypyridine-based cyan coupler described in European Patent EP 0,333,085A2 (in particular, specific examples thereof). The couplers (42) listed above as 4-equivalent couplers having a chlorine leaving group to give 2 equivalents, and couplers (6) and (9) are particularly preferred) and JP-A-64-32260. It is also preferable to use a cyclic active methylene cyan coupler (especially, coupler examples 3, 8, and 34 listed as specific examples). The processing temperature of the color developer applicable to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. Preferably, the processing time is substantially within 20 seconds. It is preferable that the replenishing amount is small, but ^{20 to} 600
ml is appropriate, preferably 50 to 300 ml. More preferably 60-200 ml, most preferably 60-15.
0 ml. In the present invention, the development time is preferably substantially within 20 seconds.
`` Second '' refers to the time from when the photosensitive material enters the developer tank to when the photosensitive material enters the next tank, and includes the time in air from the developer tank to the next tank. . The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be variously set depending on the use and characteristics of the photosensitive material, but is generally 30 to 45 ° C, preferably 35 to 42 ° C. The time can be set arbitrarily,
Shorter is desirable from the viewpoint of reduction of processing time. Preferably it is 10 to 45 seconds, more preferably 10 to 40 seconds.
The smaller the replenishment amount, the lower running cost, emission reduction,
It is preferable from the viewpoint of handleability and the like. A specific preferable replenishing amount is 0.5 to 50 times, preferably 2 to 15 times the carry-in amount from the previous bath per unit area of the photosensitive material. Alternatively, the amount is 300 ml or less, preferably 150 ml or less, per m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be used in the previous step. As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is caused to flow into a bleach-fixing bath as a preceding bath, and the bleach-fixing bath is replenished with a concentrated solution to reduce the amount of waste liquid. Next, a drying step usable in the present invention will be described. In order to complete an image by the ultra-rapid processing of the present invention, a drying time of 20 to 40 seconds is desired. As a means for shortening the drying time, a means on the photosensitive material side can be improved by reducing the amount of water carried into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is also possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. Of course, as a means for improving the dryer, it is possible to speed up the drying by increasing the temperature or increasing the drying air. Further, the drying can be expedited by adjusting the angle at which the drying air is blown to the photosensitive material or by removing the discharged air.

[0045]

【Example】

Example 1 Preparation of silver halide photographic emulsion Emulsion: An aqueous solution of 0.13 M silver nitrate and an aqueous solution of a halogen salt containing 0.04 M potassium bromide and 0.09 M sodium chloride were mixed with sodium chloride and 1,8-dihydroxy-emulsion.
In an aqueous gelatin solution containing 3,6-dithiaoctane,
While stirring, the mixture was added by a double jet method at 45 ° C. for 12 minutes to give an average grain size of 0.15 μm and a silver chloride content of 7
Nucleation was performed by obtaining 0 mol% of silver chlorobromide grains. Subsequently, a 0.87 M silver nitrate aqueous solution and 0.2
A halogen salt aqueous solution containing 6 M potassium bromide and 0.65 M sodium chloride was added by a double jet method over 20 minutes. Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added thereto.
5, adjusted to a pAg of 7.5, further added 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per mole of silver, heated at 60 ° C. for 75 minutes, subjected to chemical sensitization treatment, and used 1,3,3a, 150 mg of 7-tetrazaindene were added. The resulting grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%.
(Coefficient of variation 10%). Addition of Dye Composition An infrared dye composition which is a 10% aqueous methanol solution containing the infrared sensitizing dye and the compound represented by the general formula (I) of the present invention in the ratio shown in Table 1 was prepared. It was placed in a glass bottle and left at room temperature in the dark. Immediately after preparation from these glass bottles,
After 7 days, a predetermined amount of the composition was taken out, added to the above photographic emulsion, and subjected to spectral sensitization in the infrared region. That is, 6 moles of the dye composition per mole of the above photographic emulsion silver.
0 ml was added, and 4,4'-bis (4,6-dinaphthoxypyrimidin-2-ylamino) was added to the emulsion.
70 ml of a 0.5% methanol solution of disodium stilbene disulfonic acid and a 90% methanol solution of 2,5-dimethyl-3-allylbenzothiazole iodide 90
ml was added. In addition, hydroquinone 100mg /
m ² , polyethyl acrylate latex as a plasticizer was added at 25% by weight of gelatin, and 2-bis (vinylsulfonylacetamido) ethane was added at 86.2 mg / m ² , so that silver became 3.7 g / m ² on a polyester support. Was applied. Gelatin was 2.5 g / m ² . 0.6 g / m ² of gelatin, 60 mg / m ^{2 of} polymethyl methacrylate having a particle size of 3 to 4 μm as a matting agent, 70 mg / m ² of colloidal silica having a particle size of 10 to 20 μm
m ² , 10 mg / m ^{2 of} silicone oil, sodium dodecylbenzenesulfonate as a coating aid, an upper protective layer containing a fluorine-based surfactant having the following structural formula, gelatin 0.7 g / m ² , polyethyl acrylate Latex 225 mg / m ² , dye represented by 20 m
g / m ² , a lower layer of the protective layer to which 10 mg / m ^{2 of} a dye represented by the formula (1) and sodium dodecylbenzenesulfonate as a coating aid were added was simultaneously applied to prepare a sample.

[0046]

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[0047]

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[0048]

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The support used in this example has a back layer and a back protective layer having the compositions shown in Table 2. The swelling ratio of the back layer is 110%.

[0050]

[Table 1]

Dye D1

[0052]

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Dye D2

[0054]

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Dye a

[0056]

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Dye b

[0058]

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Dye c

[0060]

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[0061]

[Table 2]

The obtained sample was passed through an interference filter having a peak at 750 nm and a continuous wedge to emit light for an emission time of 1 hour.
Exposure with xenon flash light for 0-6 seconds, and using a developing and fixing solution shown in Table 3, an automatic developing machine FG-360F 'manufactured by Fuji Photo Film Co., Ltd. (water washing tank capacity: 6 liters)
After developing at 38 ° C. for 20 seconds, fixing, washing with water and drying, sensitometry was carried out. The reciprocal of the exposure amount giving a density of 3.0 was defined as the sensitivity, and the relative sensitivity is shown in Table 1. 50kg each sample
After standing / m in ² of pressurized air at 50 ° C. 7 days, the same photographic assessment as described above, and the results are shown in Table 1.

[0063]

[Table 3]

As is clear from Table 1, the addition of the compound represented by the general formula (I) of the present invention to the infrared sensitizing dye solution from the preparation of the dye solution to the addition to the emulsion. It can be seen that a photosensitive material with high sensitivity can be obtained stably regardless of the length of the time. In addition, it can be seen that the photosensitive material thus manufactured has little fluctuation in sensitivity during storage. Example 2 A solution having the composition shown in Table 4 and containing the compound represented by the general formula (I) of the present invention and an infrared dye was prepared, placed in a glass bottle, sealed, and placed in a dark place at room temperature. For one week. The stability of the infrared dye was compared by determining the ratio of the absorbance at the absorption maximum wavelength to the solution immediately after preparation of the solution after standing. From the results shown in Table 4, the infrared dye composition containing the compound represented by the general formula (I) of the present invention was compared with the dye solution containing no compound represented by the general formula (I) of the present invention. It can be seen that the change with time is small and the stability is improved.

[0065]

[Table 4]

Dye D3

[0067]

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Dye D4

[0069]

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──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/22 G03C 1/22 1/83 1/83

Claims (4)

[Claims] 1. A silver halide photographic material comprising a compound represented by the following general formula (I) in an amount of less than 1% by weight of silver. General formula (I) In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group or an aryl group, and at least 2
One represents a carboxyalkyl group or an alkyl ester thereof, h and i each independently represent 2 or 3, j represents 0, 1, or 2, and k represents 0 or 1. 2. The silver halide photographic light-sensitive material according to claim 1, which has a spectral sensitivity maximum wavelength longer than 700 nm. 3. A method for producing a silver halide photographic material, comprising adding a water-miscible solution containing both the compound represented by formula (I) and a dye to a silver halide emulsion. 4. A dye composition comprising a water-miscible solution containing both the compound represented by the general formula (I) and an infrared dye.