JPH07128793A - Fine solid particle dispersion of dye and silver halide photographic sensitive material containing the same - Google Patents

Abstract

PURPOSE:To obtain the fine solid particle dispersion of the dye preventing the propagation of microorganisms and superior in secular preservability by incorporating a specified compound, a dye, a surfactant, and a hydrophilic colloid. CONSTITUTION:The fine solid dye particle dispersion comprises at least one kind of compound among compounds represented by formulae I and II or the like, at least one kind of dye among dyes represented by formulae III and IV or the like, the anionic or nonionic surfactant and the hydrophilic colloid. In formulae I-IV, R1 is H, alkyl, cycloalkyl, or the like; each of R2 and R3 is, H, halogen, alkyl, or the like; each of R4 and R5 is H or alkyl; each of A and A' is an acidic group;Q is aryl or a heterocyclic group; each of L1-L3 is a methine group; m is 0 or 1; and n is 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 solid fine particle dispersion of a dye which prevents the growth of microorganisms, and a silver halide photographic light-sensitive material containing the dispersion.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials (hereinafter abbreviated as photographic light-sensitive materials) have a specific wavelength for the purpose of light absorption filter, antihalation, irradiation prevention or sensitivity adjustment of photosensitive emulsion. It is well known to incorporate a dye into a constituent layer of a photographic light-sensitive material in order to absorb the light, and dyeing a hydrophilic colloid layer with the dye has been performed.

Of the constituent layers of the photographic light-sensitive material described above, the filter layer is usually located above the light-sensitive emulsion layer or between the emulsion layer and another emulsion layer and controls incident light reaching the emulsion layer. It plays a role of changing to a preferable spectral composition. The antihalation layer is provided between the light-sensitive emulsion layer and the support or on the back surface of the support for the purpose of improving the sharpness of the image, and is harmful to the interface between the emulsion layer and the support or the back surface of the support. The reflected light is absorbed to improve the sharpness of the image. Further, it is also performed to improve the sharpness of the image by coloring the photosensitive emulsion layer with a dye to absorb harmful reflected light or scattered light to the silver halide grains to prevent irradiation. There is.

Recently, the use of dyes for dyeing a crossover cut layer in an X-ray photographic light-sensitive material, dyes for dyeing a non-light-sensitive emulsion layer in a photographic light-sensitive material for printing, and the like have been widespread.

The dye used for such purpose has not only good absorption spectrum characteristics depending on the purpose of use but also is completely decolorized during development processing and easily eluted from the photographic light-sensitive material. , No residual color contamination by dye after processing, no adverse effects such as fog or desensitization on photosensitive emulsion, no diffusion from colored layer to other layers, in photographic light-sensitive material or liquid It has to be stable over time, and it must satisfy various conditions such as not discoloring and fading.

As a means for preventing the diffusion and migration of the dye to other layers, which satisfy these various conditions, a dye whose pKa is molecularly designed to be easily dissolved in a high pH solution is used as a solid fine particle dispersion. As the body, a dye dispersed in a hydrophilic colloid layer having a low pH has been proposed. For example US patent
4,855,221, 4,857,446, 4,948,717, JP-A-5
2-92716, 55-155350, 55-155351, 56-1263
No. 9, 63-197943, JP-A-2-110453, 2-1838,
2-1839, 2-192942, 2-264247, 2-264936
No. 2, No. 2-277044, No. 4-37841, and World Patent No. 88/04794 are disclosed.

However, it is necessary to prepare and store the above dye as a solid fine particle dispersion prior to coating and manufacturing the photographic light-sensitive material. In the dispersion of the dye, a hydrophilic colloid such as gelatin or anionic polymer used as a binder of a photographic constituent layer is often added and stored, and microorganisms such as bacteria, yeast and mold are generated during storage. Was often the case. Due to the proliferation of these microorganisms, the viscosity of the coating solution decreases, the film strength of the coating layer deteriorates, and the microorganisms aggregate to form small lumps, which appear as comet-like defects during coating, Since a uniform coating layer cannot be obtained, and microbial metabolites and decomposition products adversely affect photographic characteristics, there has been a strong demand for an urgent solution.

[0008]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to solve the above-mentioned drawbacks and to provide a solid fine particle dispersion of a dye which prevents the growth of microorganisms and is excellent in storage stability over time. is there. A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a solid fine particle dispersion of a dye having an excellent coating film state.

[0009]

The above-mentioned object of the present invention can be achieved by the following constitution or.

At least one compound represented by the following general formulas (1) to (5) is 0.1 mg to 30 mg per 1 g of the dye, and at least one compound represented by the following general formulas (I) to (VI). A solid fine particle dispersion of a dye, which comprises at least one of an anionic surfactant and / or a nonionic surfactant and a hydrophilic colloid.

[0011]

[Chemical 7]

[Wherein R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carbamoyl group, a thiocarbamoyl group, or a sulfamoyl group, and R ₂ and R ₃ are each independently Represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic group, and R ₂ and R ₃ are bonded to each other. To form an aromatic ring. ]

[0013]

[Chemical 8]

[In the formula, R ₄ and R ₅ represent a hydrogen atom or an alkyl group. ]

[0015]

[Chemical 9]

[Wherein R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group or Represents a carbamoyl group, and R ₈ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a carbamoyl group or a heterocyclic group. ]

[0017]

[Chemical 10]

[Wherein R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
It represents an amino group or a carbamoyl group, and R ₉ and R ₁₀ may combine with each other to form a double bond. R ₁₂ and R
Each ₁₃ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a carbamoyl group or a heterocyclic group. ]

[0019]

[Chemical 11]

[Wherein R ₁₄ represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group or a carbamoyl group, and l
Represents an integer of 1 to 5. ]

[0021]

[Chemical 12]

[In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, and Q ′ represents a heterocyclic group. Group, X and Y, which may be the same or different, each represents an electron-withdrawing group, L ₁ , L ₂ and L ₃
Each represents a methine group. m represents 0 or 1, and n
Represents 0, 1 or 2, and p represents 0 or 1. However, the dyes represented by the general formulas (I) to (VI) have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. ] A silver halide comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of the above-mentioned dye on a support. Photographic material.

The present invention will be described in more detail below.

The dye according to the present invention is selected from the dyes represented by the following general formulas (I) to (VI).

[0025]

[Chemical 13]

[In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, and Q ′ represents a heterocyclic group. Group, X and Y, which may be the same or different, each represents an electron-withdrawing group, L ₁ , L ₂ and L ₃
Each represents a methine group. m represents 0 or 1, and n
Represents 0, 1 or 2, and p represents 0 or 1. However, the dyes represented by the general formulas (I) to (VI) have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. The acidic nuclei represented by A and A ′ in the general formulas (I), (II) and (III) are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, Examples thereof include oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and pyrazolopyridone.

The basic nucleus represented by B in the general formulas (III) and (V) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole. , Indole.

Examples of the aryl group represented by Q in the general formulas (I) and (IV) include phenyl group, naphthyl group,
Examples thereof include a julolidyl group. In addition, the general formula (I),
Examples of the heterocyclic group represented by Q and Q'of (IV) and (VI) include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group and a thienyl group. Is mentioned. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carboxy group. Group, cyano group, hydroxy group, mercapto group,
Examples thereof include an amino group, an alkoxy group, an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfonamide group, and a sulfamoyl group, and these substituents may have two or more kinds in combination. As a preferable substituent, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, t-butyl group, octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, Halogen atom (eg, fluorine atom, chlorine atom, etc.), C1-C6 alkoxy group (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, butoxy group, etc.), substituted amino group (eg, dimethyl group) Amino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), Carboxy group, sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, sulfamoyl group) Group, methylsulfamoyl group,
Phenylsulfamoyl group), and these substituents may be combined.

The electron-withdrawing groups represented by X and Y in the general formulas (IV) and (V) may be the same or different, and the σp value of the substituent constant Hammett (edited by Toshio Fujita, “Chemical Domain”). Special Issue No. 122, Structure-Activity Relationship of Drugs, pp. 96-103 (1
979) It is described in Nankodo and other places. ) Is 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-hydroxy group). Phenoxycarbonyl group), carbamoyl group (eg carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg methylcarbonyl group, ethyl Carbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group) , Butylsulfonyl group, an octyl sulfonyl group, etc.), an arylsulfonyl group (e.g., phenylsulfonyl group, 4-chlorosulfonyl group, etc.).

L ₁ , L ₂ and L _{3 of the} general formulas (I) to (V)
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group (for example, a phenyl group). , Tolyl group, 4-hydroxyphenyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.), heterocyclic group (eg pyridyl group, furyl group,
And a substituted amino group (eg, dimethylamino group, diethylamino group, anilino group, etc.), and alkylthio group (eg, methylthio group, etc.).

In the present invention, among the dyes represented by the general formulas (I) to (VI), those having at least one carboxy group in the molecule are preferably used, and more preferably the general formula (I) A dye represented by the formula, and particularly preferably a dye in which Q in the general formula (I) is a furyl group.

Next, specific examples of the dye used in the present invention will be given.

[0033]

[Chemical 14]

[0034]

[Chemical 15]

[0035]

[Chemical 16]

[0036]

[Chemical 17]

[0037]

[Chemical 18]

[0038]

[Chemical 19]

[0039]

[Chemical 20]

[0040]

[Chemical 21]

[0041]

[Chemical formula 22]

[0042]

[Chemical formula 23]

[0043]

[Chemical formula 24]

[0044]

[Chemical 25]

Specific examples of the dye used in the present invention are further described in JP-A-52-92716, JP-A-55-120030, and JP-A-55-155350.
55-155351, 56-12639, 63-197943, JP
No. 2-1838, No. 2-1839, World Patent 88/04794, U.S. Patent Nos. 4,861,700, No. 4,950,586, European Patent 489,973, etc., and the synthesis method is also described in these patents. It can be synthesized according to the method. A specific synthesis example is shown below.

Synthesis Example 1 (Exemplified Dye I-4) 1- (4-Carboxyphenyl) -3-cyano-5-pyrazolone 11.5
7.5 g of g, 4-dimethylaminobenzaldehyde and 6.0 g of pyridine were placed in a mixed solvent of 200 ml of methanol and 20 ml of dimethylformaldehyde and reacted at room temperature for 3 days.
The precipitate was collected by filtration and washed well with methanol. The crude crystals were dissolved in 240 ml of methanol, 100 ml of distilled water and 7.0 g of triethylamine, and then 20.0 g of acetic acid was added to cause precipitation. The precipitate was collected by filtration, washed thoroughly with methanol, and dried to obtain 9.2 g of dye (I-4). The structure of the compound is NMR, IR
And MASS spectrum.

Synthesis Example 2 (Exemplary Dye I-15) 1- (4-Carboxyphenyl) -3-cyano-5-pyrazolone 45.8
27.8 g of g, 5-dimethylaminofurfural and 23.7 g of pyridine were placed in a mixed solvent of 800 ml of methanol and 80 ml of dimethylformaldehyde and reacted at room temperature for 4 days. The precipitate was collected by filtration and washed well with methanol. The crude crystals were dissolved in 1000 ml of methanol, 250 ml of distilled water and 16.0 g of triethylamine, and then 40.0 g of acetic acid dissolved in 100 ml of methanol was added for precipitation. The precipitate was collected by filtration, washed thoroughly with methanol, and dried to obtain 42.0 g of dye (I-15). The structure of the compound was confirmed by NMR, IR and MASS spectra.

A method for producing a solid fine particle dispersion of a dye according to the present invention is described in JP-A-52-92716 and JP-A-55-15535.
No. 0, 55-155351, 63-197943, 3-182743
The method described in Japanese Patent No. WO88 / 04794 and the like can be used. Specifically, it can be prepared by using a surfactant and using a fine disperser such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill or a disc impeller mill. Further, after dissolving the dye in a weak alkaline aqueous solution, a method of precipitating fine particulate solids by lowering the pH to weakly acidic or a weak alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. Dispersions of dyes can be obtained by the method of making finely divided solids. The dyes may be used alone or in combination of two or more.
When two or more kinds are mixed and used, they may be dispersed individually and then mixed, or may be simultaneously dispersed.

The dye dispersed in the form of solid fine particles according to the present invention is preferably dispersed so that the average particle size is 0.01 μm to 5 μm, more preferably 0.01 μm to 1 μm, and particularly preferably 0.01 μm. ~ 0.5 μm. Also,
The coefficient of variation of particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (Average value of particle size) × 100 In the solid fine particle dispersion of the dye according to the present invention, at least one compound represented by the general formulas (1) to (5) is used. Contains. In the general formulas (1) to (5), an alkyl group,
The alkyl moiety of the alkenyl group, alkylthio group, alkylsulfonyl group, alkoxy group and alkoxycarbonyl group has 1 to 30, preferably 1 to 18 and more preferably 1 to 12 carbon atoms. The number of carbon atoms in the cycloalkyl group is 3 to
6 is preferred. Examples of the aryl group and arylthio group, arylsulfonyl group, aryloxy group, and aryl moiety of the aryloxy group include phenyl group and naphthyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the carbamoyl group include a carbamoyl group, a methylcarbamoyl group, an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, a dodecylcarbamoyl group,
Examples thereof include a dimethylcarbamoyl group and a phenylcarbamoyl group. Examples of the thiocarbamoyl group include an aminothiocarbamoyl group, a methylthiocarbamoyl group, an ethylthiocarbamoyl group, a propylthiocarbamoyl group, a burthiocarbamoyl group, a dodecylthiocarbamoyl group, a dimethylthiocarbamoyl group and a phenylthiocarbamoyl group. Examples of the sulfamoyl group include a sulfamoyl group, a methylsulfamoyl group, an ethylsulfamoyl group, a propylsulfamoyl group, a butylsulfamoyl group, a dodecylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group. Etc. Examples of the amino group include an amino group, a methylamino group, an ethylamino group, an octylamino group, a dimethylamino group, an anilino group, a morpholino group, and a piperazino group. Examples of the heterocyclic group include a furyl group, a thienyl group, a pyridyl group, an oxazolyl group, an imidazolyl group and a pyrazolyl group. Each of these groups includes those having a substituent, and examples of the substituent include the aryl group represented by Q in the general formulas (I) and (IV) and the substituents represented by the heterocyclic group. There are things. Specific examples of the compound used in the present invention are shown below.

Representative specific examples of the compound represented by the general formula (1) are shown below.

(1) -1 1,2-benzisothiazolin-3-one (1) -2 2-methyl-1,2-benzisothiazolin-3-one (1) -3 2-ethyl-1,2- Benzisothiazolin-3-one (1) -4 2- (Propyl) -1,2-benzisothiazolin-3-one (1) -5 2- (Butyl) -1,2-benzisothiazolin-3-one (1 ) -6 2- (sec-Butyl) -1,2-benzisothiazoline-3-
On (1) -7 2- (t-butyl) -1,2-benzisothiazolin-3-one (1) -8 2-methoxy-1,2-benzisothiazolin-3-one (1) -9 2- Ethoxy-1,2-benzisothiazolin-3-one (1) -10 2- (propyloxy) -1,2-benzisothiazolin-3-one (1) -11 2- (butyloxy) -1,2-benzo Isothiazoline-
3-one (1) -12 5-chloro-1,2-benzisothiazolin-3-one (1) -13 5-methyl-1,2-benzisothiazolin-3-one (1) -14 6-ethoxy- 1,2-Benzisothiazolin-3-one (1) -15 6-Cyano-1,2-benzisothiazolin-3-one (1) -16 5-Nitro-1,2-benzisothiazolin-3-one (1 ) -17 2- (N-Methylcarbamoyl) -1,2-isothiazolin-3-one (1) -18 5-Methyl-2- (N-methylcarbamoyl) -1,2-isothiazolin-3-one (1 ) -19 2- (N-Methylthiocarbamoyl) -1,2-isothiazolin-3-one (1) -20 4-Bromo-5-methyl-2- (N-methylcarbamoyl)
-1,2-Isothiazolin-3-one (1) -21 4-cyano-5-methylthio-2- (N-methylcarbamoyl) -1,2-isothiazolin-3-one (1) -22 4-cyano- 5-Methylsulfinyl-2- (N-methylcarbamoyl) -1,2-isothiazolin-3-one (1) -23 4-Cyano-5-methylsulfonyl-2- (N-methylcarbamoyl) -1,2- Isothiazolin-3-one (1) -24 2- (Nn-butylcarbamoyl) -1,2-isothiazolin-3-one (1) -25 2- (Nt-octylcarbamoyl) -1,2-isothiazolin-3- One (1) -26 5-Methyl-2- (N-phenylcarbamoyl) -1,2-isothiazolin-3-one (1) -27 4-Cyano-5-methylthio-2- (N-phenylcarbamoyl)- 1,2-Isothiazolin-3-one (1) -28 4-Bromo-5-methyl-2- (N-3-chlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -29 4-Bromomethyl -2- (N-3-chlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -30 5-methyl-2- (N-3-chlorophene Lucarbamoyl) -1,2-isothiazolin-3-one (1) -31 4-cyano-5-methylthio-2- (N-3-chlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -32 2- (N-3-chlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -33 5-methyl-2- (N-2-chlorophenylcarbamoyl) -1,2-isothiazolin-3-one ( 1) -34 5-Bromomethyl-2- (N-2-chlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -35 4-Bromo-5-methyl-2- (N-3,4- Dichlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -36 5-methyl-2- (N-3,4-dichlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -37 4 -Cyano-5-methylthio-2- (N-3,4-dichlorophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -38 5-methyl-2- (N-4-tosylcarbamoyl) -1 , 2-Isothiazolin-3-one (1) -39 4-cyano-5-methylthio-2- (N-4-tosylcarbamoyl) -1, 2-Isothiazolin-3-one (1) -40 2- (N-propylcarbamoyl) -1,2-isothiazolin-3-one (1) -41 2- (N-ethylcarbamoyl) -1,2-isothiazolin- 3-one (1) -42 2- (Ni-propylcarbamoyl) -1,2-isothiazolin-3-one (1) -43 4-bromo-2- (N-methylcarbamoyl) -1,2-isothiazoline- 3-one (1) -44 2- (N-4-methoxyphenylcarbamoyl) -1,2-
Isothiazolin-3-one (1) -45 2- (N-2-methoxyphenylcarbamoyl) -1,2-
Isothiazolin-3-one (1) -46 2- (N-3-nitrophenylcarbamoyl) -1,2-isothiazolin-3-one (1) -47 2- (N-3,4-dichlorophenylcarbamoyl) -1 , 2
-Isothiazolin-3-one (1) -48 2- (Nn-dodecylphenylcarbamoyl) -1,2-
Isothiazolin-3-one (1) -49 2- (N-2,5-dichlorophenylcarbamoyl) -1,2
-Isothiazolin-3-one (1) -50 2- (N-carboethoxycarbamoyl) -1,2-isothiazolin-3-one (1) -51 2- (N-4-nitrophenylcarbamoyl) -1,2 -Isothiazolin-3-one (1) -52 5-methyl-2- (N-ethylcarbamoyl) -1,2-isothiazolin-3-one (1) -53 5-methyl-2- (N-ethylthiocarbamoyl) ) -1,2-
Isothiazolin-3-one (1) -54 5-chloro-2- (N-ethylcarbamoyl) -1,2-isothiazolin-3-one (1) -55 2-n-propyl-1,2-isothiazolin-3 -One (1) -56 2-i-propyl-1,2-isothiazolin-3-one (1) -57 2-n-butyl-1,2-isothiazolin-3-one (1) -58 2-t -Butyl-1,2-isothiazolin-3-one (1) -59 2-Cyclohexyl-1,2-isothiazolin-3-one (1) -60 2-octyl-1,2-isothiazolin-3-one (1 ) -61 2-t-octyl-1,2-isothiazolin-3-one (1) -62 2-benzyloxy-1,2-isothiazolin-3-one (1) -63 3-chloro-2-methyl- 1,2-Isothiazolin-3-one (1) -64 3-chloro-2-benzyl-1,2-isothiazolin-3-
On (1) -65 4,5-dichloro-2-methyl-1,2-isothiazoline-3
-One (1) -66 2,4-dimethyl-1,2-isothiazolin-3-one (1) -67 4-methyl-2- (3,4-dichlorophenyl) -1,2-isothiazolin-3-one (1) -68 2- (3,4-Dichlorophenyl) -1,2-isothiazolin-3-one (1) -69 4,5-Dichloro-2-benzyl-1,2-isothiazoline
-3-one (1) -70 4-bromo-5-chloro-2-methyl-1,2-isothiazolin-3-one (1) -71 4-bromo-2-methyl-1,2-isothiazoline-3 -One (1) -72 2-hydroxymethyl-1,2-isothiazolin-3-one (1) -73 2- (2-diethylaminoethyl) -1,2-isothiazolin-3-one (1) -74 2 -Propyl-1,2-isothiazolin-3-one hydrochloride (1) -75 5-chloro-2-methyl-1,2-isothiazolin-3-one hydrochloride (1) -76 2-ethyl-1,2 -Isothiazolin-3-one hydrochloride (1) -77 2-methyl-1,2-isothiazolin-3-one hydrochloride (1) -78 2-benzyl-1,2-isothiazolin-3-one hydrochloride (1 ) -79 2-Dodecyl-1,2-isothiazolin-3-one (1) -80 2-Tetradecyl-1,2-isothiazolin-3-one (1) -81 2- (2-chlorobenzyl) -1, 2-isothiazoline-3-
One (1) -82 2- (2,4-Dichlorobenzyl) -1,2-isothiazolin-3-one (1) -83 2- (3,4-Dichlorobenzyl) -1,2-isothiazolin-3- ON (1) -84 2- (4-methoxybenzyl) -1,2-isothiazoline-
3-one (1) -85 2- (4-methylbenzyl) -1,2-isothiazoline-3-
ON (1) -86 2- (2-Ethoxyhexyl) -1,2-isothiazoline-
3-one (1) -87 2- (2-phenylethyl) -1,2-isothiazoline-3-
On (1) -88 2- (2-Phenylethyl) -4-chloro-1,2-isothiazolin-3-one (1) -89 2- (1-Phenylethyl) -1,2-isothiazoline-3-
ON (1) -90 2- (1-phenylethyl) -1,2-isothiazoline-3-
On (1) -91 2-t-octyl-4-chloro-1,2-isothiazoline-3
-One (1) -92 2-t-octyl-4-bromo-1,2-isothiazoline-3
-One (1) -93 2-octyl-4-bromo-1,2-isothiazoline-3-
On (1) -94 2- (4-nitrophenyl) -1,2-isothiazoline-3-
One (1) -95 2- (4-Carboethoxyphenyl) -1,2-isothiazolin-3-one (1) -96 5-Chloro-2-methyl-1,2-isothiazolin-3-one monochloroacetic acid Salt (1) -97 4,5-Dichloro-2-methyl-1,2-isothiazoline-3
-One monochloroacetic acid salt (1) -98 2-Ethyl-1,2-isothiazolin-3-one monochloroacetic acid salt (1) -99 2-Benzyl-1,2-isothiazolin-3-one monochloroacetic acid salt Further, among the compounds represented by the general formula (1), particularly preferable ones include the following compounds.

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

These compounds are, for example, French patents 1,
It can be synthesized by the method described in the specification of 555,416 or the like or a method similar thereto.

Representative specific examples of the compound represented by the general formula (2) are shown below.

[0057]

[Chemical 28]

The above compounds are easily available as commercial products.

Typical specific examples of the compounds represented by the general formulas (3) and (4) are shown below.

[0060]

[Chemical 29]

[0061]

[Chemical 30]

[0062]

[Chemical 31]

These compounds are readily available as commercial products, and are also available in Chemical Pharmacy Bulletin (Chem. Pharm. Bull.) Vol. 32, No. 2, 733.
~ 738 pages, Journal of American Chemicals
Society (Journal of American Chemical Socie
ty) Vol. 79, No. 10, pp. 4558-4559 or Japanese patent 99
It can be synthesized by the method described in No. 1,641 or the like or a method analogous thereto.

Representative specific examples of the compound represented by the general formula (5) are shown below.

[0065]

[Chemical 32]

The conditions for preserving the solid fine particle dispersion of the dye used in the photographic light-sensitive material are as follows: no interaction with photographic additives, small amount against microorganisms such as bacteria, yeast and mold. It is a highly effective antibacterial and antifungal agent, has no effect on photographic performance such as desensitization, fog, graininess and sharpness, and has no effect on photographic processing performance such as developability and fixability. Is mentioned.

The amount of the compounds represented by the general formulas (1) to (5) to be used is not uniform depending on the kind of the compound or the conditions of the dispersion liquid of the dye, but it is usually 0.01 to 50 mg per 1 g of the dye. Well, preferably 0.05-40 mg,
More preferably, it may be 0.1 to 30 mg. The concentration of the dye in the dispersion is used to be 1 to 1000 ppm,
It is preferably 5 to 500 ppm. These compounds may be used alone or in combination of two or more kinds.

Upon addition, the compound itself may be added as it is, or it may be added after being dissolved in water or a hydrophilic organic solvent such as methanol, ethanol, acetone or methyl cellosolve. The addition position is
It may be added before the dispersion of the dye is started, or if necessary, it may be added together with other additives to the dye dispersion after the dispersion is completed.

Any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used as the surfactant according to the present invention.
Preferred are, for example, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines. And anionic surfactants such as saponins, alkylene oxide derivatives, and nonionic surfactants such as alkyl esters of sugars. The above-mentioned anionic surfactants are particularly preferable. Specifically, the following surfactants are preferably used.

[0070]

[Chemical 33]

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36]

[0074]

[Chemical 37]

[0075]

[Chemical 38]

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, but usually the dye 1 is used.
It may be 0.1 to 2000 mg, preferably 0.5 to 1000 mg, and more preferably 1 to 500 mg per g. The concentration of the dye in the dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight. The surfactant may be added at a position before the dispersion of the dye is started, and if necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic activator and / or nonionic activator may be used alone,
In addition, two or more kinds may be used in combination, and both activators may be used in combination.

To the dye dispersion of the present invention, a hydrophilic colloid used as a binder for a photographic constituent layer can be added before the start of dispersion or after the end of dispersion. As the hydrophilic colloid, it is advantageous to use gelatin, but in addition, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin and phthalated gelatin, and gelatin and a monomer having a polymerizable ethylene group can be used. Graft polymers, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-
Synthetic hydrophilic polymers such as N, N-dimethylacrylamide, poly-N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. You may use these in combination of 2 or more types. The amount of the hydrophilic colloid added to the dye dispersion of the present invention is preferably 0.1 to 12% by weight, more preferably 0.5.
~ 8% by weight.

The dispersion of the dye of the present invention is a layer constituting a photographic light-sensitive material such as a light-sensitive silver halide emulsion layer, an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer and a backing layer. Can be used for. The preferred amount of the dye is not uniform depending on the type of the dye and the characteristics of the photographic light-sensitive material, but is 1 mg to 1 g per 1 m ^{2 of} the photographic light-sensitive material,
More preferably 5 mg to 800 mg, particularly preferably 10 m
g to 500 mg.

The photographic light-sensitive material of the present invention may have at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of the support, and A photographic light-sensitive material having the emulsion layer and the colloid layer on both sides of the support is also preferably used. Photographic materials include medical X-ray photographic materials, printing plate photographic materials, color negative photographic materials, color reversal photographic materials, color photographic paper photographic materials, direct positive photographic materials, and heat-developable color photographic materials. , Diffusion transfer type color photographic materials and the like.

In the photographic light-sensitive material of the present invention, the solid fine particle dispersion of the dye may be contained in at least one non-photosensitive hydrophilic colloid layer. Gelatin is preferably used as the hydrophilic colloid layer, but when the solid fine particle dispersion of the dye is contained in the non-photosensitive hydrophilic colloid layer, the hydrophilic colloid coating amount is 0.05 g / m ^{2 to} 1.5 g / m ²
Is preferred, and more preferably 0.1 g / m ² ~
It is 1.2 g / m ² .

The halogenated emulsion used in the photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Although any of silver chloroiodobromide, silver chloride and the like can be used, silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide are particularly preferable.

The silver halide grains in the photographic emulsion are all isotropically grown crystal types such as cubes, octahedra and tetrahedra, or polyhedral crystal types such as spheres, and plane defects. It may be of a twin crystal having, or a mixed type or a composite type thereof. The grain size of these silver halide grains may be from fine grains of 0.1 μm or less to large grains of 15 μm.

The emulsion used in the photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), pages 22-23
1; Emulsion Preparation and Types and No. 18716 (November, 1979), p.648. Also, TH James's “The Theory of the Photographic Process” (The t
heory of the photographic process, 4th edition, published by Macmillan (1977), pages 38-104, GF Dauffin, "Photoemulsion Chemistry" (Pho
tographic Emulsion Chemistry) Focal Press (1966), P. Graph Kids (Glafk)
ides) "Physics and Chemistry of Photography" (Chimie et Physique P
hotographique, published by Paul Montel (1967), VL Zelikman, et al. "Making and Coating Photograp"
hic Emulsion), Focal Press
It is prepared by the method described in the company publication (1964). In other words, particle preparation such as forward mixing method, back mixing method, double jet method, controlled double jet method, etc., conversion method, core / shell method, etc. under solution conditions such as neutral method, acidic method, ammonia method, etc. It can be manufactured using conditions and combinations of these.

The silver halide emulsions preferably used in the present invention are, for example, JP-A-59-177535 and 61-802238.
No. 61-132943, No. 63-49751, and the like, high internal iodine type monodisperse particles are disclosed. The crystal habit may be a cube, an octahedron, a tetrahedron, or an intermediate (111) plane and (100) plane mixed arbitrarily. The monodisperse emulsion referred to here is a halogen having at least 95% of the grains by number or weight within ± 40% of the average grain size, preferably within ± 30% when the average grain diameter is measured by a conventional method. It is a silver halide grain. The grain size distribution of the silver halide grains may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The definition of monodispersity described here is described in JP-A-60-162244, and the coefficient of variation with respect to particle diameter is 0.2 or less.
The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. For example, a core / shell type monodisperse emulsion having a two-layer structure composed of a high-iodity core portion and a low-iodity shell layer can be mentioned. A method for producing a monodisperse emulsion is known, for example, JP-A-48-36890 and JP-A-52-16364.
Nos. 55-142329, 58-49938, 60-14331, British Patents 1,027,146, 1,413,748, U.S. Patents 3,505,06.
No. 8, No. 3,574,628, No. 3,655,394, No. 4,444,877 and the like.

The silver halide emulsion preferably used in the present invention includes tabular grains having an aspect ratio of 3 or more. The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness. For example, British Patent 2,112,157 and U.S. Pat.
Issue 4,433,048, Issue 4,414,310, Issue 4,434,226,
JP-A-58-113927, 58-127921, 63-138342,
No. 63-284272, No. 63-305343, etc.,
The emulsion can be produced by the methods described in these publications. The tabular silver halide grains according to the present invention are preferably monodisperse emulsions having a narrow grain size distribution, and the coefficient of variation is preferably 25% or less, more preferably 20% or less, particularly preferably 15%. % Or less. As tabular silver halide grains, at least 80% or more of the total projected area of silver halide grains contained in the emulsion should have an aspect ratio of 3.0 to 12.0 indicated by the (grain size) / (thickness) ratio. Is preferred, and more preferably the aspect ratio is 3.
0 to 8.0. The thickness of tabular silver halide grains is 0.05.
˜1 μm, more preferably 0.05
~ 0.5 μm. If the average of the ratio (t / l) of the longest distance (l) between two or more parallel twin planes of the tabular silver halide grain and the thickness (t) of the tabular grain is 5 or more, It is preferably, and more preferably 7 or more.
The tabular silver halide grains preferably used are core /
Shell type grains having, for example, a double structure type grain having a silver halide composition whose surface is different from the grain interior.
Examples thereof include multi-structured particles shown in No. 151 and the like.

In order to control the growth of grains during the formation of silver halide grains, it is possible to use, for example, ammonia, a thioether compound or a thione compound as a silver halide solvent. Also, during physical aging and chemical aging, zinc,
A metal salt such as lead, thallium, iridium or rhodium can coexist.

The above silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, reduction sensitization can be performed, and these methods can be combined for sensitization.

The photographic light-sensitive material of the present invention can be obtained by coating an emulsion prepared by dispersing the above silver halide in a hydrophilic colloid medium, for example, in gelatin on a polyethylene terephthalate or triacetate cellulose support.
For the cross-linking of gelatin, aldehydes such as glyoxal and mucochloric acid, cyanuric acid, aziridine, vinyl sulfones and the like can be used.

If necessary, various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention. For example, in addition to the photosensitive silver halide emulsion layer, an auxiliary layer such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, a backing layer, etc. can be provided. , Supersensitizer,
Coupler, high boiling solvent, antifoggant, stabilizer, development inhibitor, bleaching accelerator, fixing accelerator, color mixing inhibitor, formalin scavenger, toning agent, hardener, surfactant, thickener, plasticizer, A slip agent, an ultraviolet absorber, a polymer latex, an antistatic agent, a matting agent and the like can be incorporated by various methods. As a support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose triacetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, polyethylene laminated paper, etc. Glass, metal, etc. can also be used.
The surface of these supports is provided with an undercoat layer to improve the adhesion of the coating layer, or is subjected to an undercoating process such as corona discharge or ultraviolet irradiation as required.

These additives described above are described in more detail in Research Disclosure No. 17643 (December 1978).
No. 18716 (November 1979), No. 308119 (December 1989)
Month). The types of compounds shown in these Research Disclosures and their locations are shown below.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. The Theory of the Photographic Process by James, Part 4
Edition (The Theory of the Photographic Process, fourth
Edition) 291-334 and the Journal of the American Chemical Society
rican Chemical Society) Vol. 73, page 3,100 (1951), the developer can be effectively used.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 648 Upper right 996 Sensitizing dye 23 648-649 996-8 Desensitizing dye 23 998 B Dye 25-26 649-650 1003 Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 649 Upper right 1006-7 Whitening agent 24 998 Hardener 26 651 Left 1004-5 Surfactant 26-27 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 XXII Support 28 XVII 1009 XVII

[0093]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Solid Fine Particle Dispersion of Dye) The following method (1),
According to (2), solid fine particle dispersions of the dyes shown in Table 1 were prepared.

(1) It was manufactured according to the method described in World Patent 88/04794. In a 60 ml screw cap container,
21.7 ml water and surfactant Triton X-200 (Rohm & Haas
2.65 g of a 6.7% solution (made by the company) was added, 1.0 g of the dye powdered in a mortar was added to this solution, and 40 ml of zirconium oxide beads (2 mm diameter) was added. After closing the cap and placing on a ball mill and dispersing at room temperature for 4 days, 8.0 g of 12.5% gelatin aqueous solution and 1% aqueous solution of the compound shown in Table 1 (addition amount shown in Table 1) were added and mixed well, and zirconium oxide was added. The beads were filtered off and a solid fine particle dispersion of the dye was obtained.

(2) 150 g of 4% gelatin and the surfactant Trito
3.0 g of a 6.7% solution of nX-200 (Rohm & Haas) and 10.0 ml of a 1N aqueous citric acid solution were added, and the mixture was kept at 40 ° C. With stirring, a dye solution prepared by dissolving 6.0 g of dye in 5 ml of 1N sodium acetate and 25 ml of water was added to this solution by a tube pump at a speed of 5 ml per minute. After addition
Stirring was continued for 1 hour, and a 1% aqueous solution of the compound shown in Table 1 (addition amount shown in Table 1) was added to obtain a solid fine particle dispersion of the dye.

Solid fine particle dispersions of the dyes shown in Table 1 were dispensed into petri dishes, and each sample was subjected to Acinetobacter genus, Entrobacte (Entrobacte).
r) and Psudomonas spp. were inoculated and cultured at 25 ° C for 21 days, and the mold growth state of each sample was observed. The mold growth condition was evaluated visually by the following criteria.

◯: No mold spores were observed at all Δ: Only mold spores were observed slightly ×: Mold spores and spores were considerably grown. The results obtained are shown in Table 1.

[0099]

[Table 1]

It can be seen from Table 1 that the solid fine particle dispersion of the dye according to the present invention has no mold growth and has a great antifungal effect.
It can be seen that the storage stability with time is excellent.

Example 2 A solid fine particle dispersion of each dye prepared in Example 1 was added to the genus Acinetobacter, Entropobacter (E).
After inoculating a mixed bacterial solution of the genus ntrobacter) and the genus Psudomonas, the mixture was shake-cultured at 37 ° C for 20 hours. A 1N sodium carbonate aqueous solution containing 5 wt% sodium sulfite was added to each sample to dissolve the dye, and the number of microorganisms was observed. The evaluation of the generation status of microorganisms was performed visually by the following criteria.

◯: The solution is transparent and no microorganisms are observed. Δ: The solution is turbid, and the generation of microorganisms is slightly observed. ×: The solution is suspended and microorganisms are considerably observed. Result obtained Is shown in Table 2.

[0103]

[Table 2]

From Table 2, it can be seen that the solid fine particle dispersion of the dye according to the present invention has a great effect of suppressing the growth of microorganisms.

Example 3 On a transparent polyethylene terephthalate film support having a thickness of 100 μm and subjected to a subbing process, gelatin 0.5 g /
m ² , hardening agent: 1,2-bis (vinylsulfonylacetamide) ethane 0.04 g / m ² , surfactant: sodium-i-amyl-decylsulfosuccinate 0.06 g / m ² and solids shown in Table 3. Dye in which fine particles are dispersed: Coating was performed so as to be 0.1 g / m ² . A solid fine particle dispersion of a dye was prepared by the dispersion method (1) described in Example 1,
After storing for 7, 15, 30 days, it was used for preparing a coating solution. The coating solution was applied after being stagnated at 40 ° C. for 1 hour after preparation.

The film state of the coated product was evaluated visually by the following criteria.

◯: No coating unevenness was observed, and the coating was uniform and good. Δ: A few coating unevennesses were observed, which may be a problem in practical use. ×: Many coating unevenness occurred, which was not practical. Table 3 shows the obtained results.

[0108]

[Table 3]

From Table 3, it can be seen that the solid fine particle dispersion of the dye according to the present invention can give a coated material in an excellent film state even after being used after storage with time.

Example 4 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropylene oxy-polyethylene oxydisuccinate Na salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 824 ml iodide Potassium 23.5 g Water 2825 ml D1 1.75N Potassium bromide aqueous solution Solution A1 solution B1 and solution A1 at the following silver potential control amount 35 ° C. using a mixing stirrer as shown in Japanese Patent Publication Nos. 58-58288 and 58-58289. Solution C
Nucleation was carried out by adding 464.4 ml each of 1 by the double-sided mixing method over 2 minutes.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 5.0 with 3% potassium hydroxide, and then re-solution. B1 and solution C1 were mixed by the simultaneous mixing method to give 55.4 each.
It was added for 42 minutes at a flow rate of ml / min. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 35 ° C. to 60 ° C. and simultaneous mixing with the solutions B1 and C1 was +8 mv and, respectively, using the solution D1. Controlled to be + 16mv. After the addition was completed, the pH was adjusted to 6 with 3% potassium hydroxide, and the mixture was immediately desalted and washed with water.

In this seed emulsion, 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains had an average thickness of 0.06 μm and an average grain size ( It was confirmed by an electron microscope that the circle diameter was 0.59 μm.

(Preparation of Emulsion Em-1) Tabular emulsion Em-1 was prepared using seed emulsion-1 and the following three kinds of solutions.

A2 ossein gelatin 5.26 g polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-1 equivalent to 0.094 mol 569 ml B2 ossein gelatin 15.5 g potassium bromide 114 g potassium iodide 3.19 g Water 658 ml C2 Silver nitrate 166 g Water 889 ml To solution A2 vigorously stirred at 60 ° C., solution B2 and solution C2 were added in 107 minutes by the double jet method. During this time, the pH is 5.8
In addition, pAg was kept at 8.7 throughout. The addition rates of solution B2 and solution C2 were linearly increased to 6.4 times in the initial and final stages. After the addition was completed, in order to remove excess salts, precipitation desalting was performed using an aqueous solution of demole (manufactured by Kao Atlas Co.) and an aqueous solution of magnesium sulfate, and pAg 8.5 at 40 ° C.
An emulsion having an average silver iodide content of pH 5.85 of about 2.0 mol% was obtained.

Observation of the obtained emulsion with an electron microscope revealed that 82% of the projected area was tabular silver halide grains having an average grain size of 0.98 μm, a grain size distribution of 15% and an average aspect ratio of 4.5. there were. The average of the ratio (t / l) between the distance between twin planes (l) and the thickness (t) of the tabular grains was 11.
The crystal planes consisted of (111) and (100) planes, the main planes were all (111) planes, and the ratio of (111) planes to (100) planes at the edge plane was 78:22.

This emulsion Em-1 was adjusted to pH 5.8 and pH 7.0 with citric acid and sodium chloride, and then sensitizing dye (A) 4.0 × 10 ⁻⁴ mol / mol silver and sensitizing dye ( B) 4.0 x
^10-6 mol / mol silver was added, and after 10 minutes, optimum chemical ripening was performed at 60 ° C. with ammonium thiocyanate, sodium thiosulfate pentahydrate and chloroauric acid, and then 4′-hydroxy-6-methyl. The ripening was stopped by adding 1.0 g of 1,3,3a, 7-tetrazaindene per mol of silver. The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution.

[0118]

[Chemical Formula 39]

Preparation of Emulsion Coating Solution Additives used in Emulsion Em-1 are as follows. The addition amount is indicated by the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butylcatechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1, Ammonium 3-dihydroxybenzene-4-sulfonate 2g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5g

[0121]

[Chemical 40]

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg Preparation of protective layer coating liquid Next, the following was prepared as a protective layer coating liquid. did. The added amount is shown as an amount per 1 liter of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size of 1.2 μm Matting agent) 0.5g Ludox AM (manufactured by DuPont) (colloidal silica) 30g (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ ) ₂ (hardener) 500mg C ₄ F ₉ SO ₃ K 2mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0124]

[Chemical 41]

Preparation of photographic light-sensitive material A blue-colored polyethylene terephthalate support having a thickness of 175 μm, which was subjected to an undercoating process according to the method of Sample No. 9 of Example 1 of JP-A-52-104913, had the following composition. The crossover cut layer was applied as described above. A dispersion of the dye was prepared by the dispersion method (1) described in Example 1,
It was stored at 25 ° C for 14 days and then used as a coating solution.

(Crossover Cut Layer) Gelatin 0.4 g / m ² Polyvinylpyrrolidone (molecular weight 10,000) 0.1 g / m ² Sodium-i-amyl-decylsulfosuccinate 0.04 g / m ² Dye dispersion according to the present invention. Description (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ ) ₂ (hardener) 0.03 g / m ² Next, using the emulsion coating solution and the protective layer coating solution, the amount of silver in the emulsion layer was 1.9 g / m ² per side. , As the amount of gelatin
2.0 g / m ^2, two-sided simultaneous coating at a speed per minute 80m using a slide hopper type coater so that 1.1 g / m ² as the amount of gelatin protective layer, and dried at 2 minutes 20 seconds, Table 4 A sample (photographic light-sensitive material for X-ray) shown in was prepared.

[Evaluation of Photographic Performance] The obtained sample was sandwiched between two intensifying screens (KO-250), and a tube voltage of 80 kvp, a tube current of 100 mA, and an X-ray of 0.05 seconds were irradiated through an aluminum wedge, Exposed. Next, an automatic processor SRX-502 (made by Konica) for rapid processing, in which a developing solution and a fixing solution having the composition shown below were added.
Was processed under the following conditions. Optical densitometer for processed samples
The density was measured with PDA-65 (manufactured by Konica), and the sensitivity, fog and gamma were obtained. The sensitivity was calculated by taking the reciprocal of the exposure amount at the fog density + 0.1, and shown as a relative value with the sensitivity immediately after coating and drying of sample No. 1 in Table 4 taken as 100. Gamma is represented by the slope of the straight line portion of the characteristic curve.

<Preparation of Treatment Agent> (Developer formulation) Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% aqueous solution) 2280 g Sodium hydrogencarbonate 132 g Diethylenetetraamine pentaacetic acid 120 g 5-Methylbenzo Triazole 1.2 g 1-Phenyl-5-mercaptotetrazole 1.2 g Hydroquinone 340 g Add water to finish to 5.0 l Part-B (for 12 liter finish) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitro Indazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1.0 l Add Part-A and Part-B above to about 5 l of water at the same time, make 12 l with water while stirring, and add pH to glacial acetic acid. Was adjusted to 10.4. This is used as a development replenisher. 1 liter of this developer replenisher
On the other hand, 20 ml of the above-mentioned starter was added and the pH was adjusted to 10.26 to prepare a developing solution.

(Fixing solution formulation) Prat-A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) ) -Ethyl-5-mercaptotetrazole 18g Prat-B (for 18l finishing) Aluminum sulphate (anhydrous salt equivalent) 800g Part-A and Part-B are added at the same time to about 5l of water, and water is added with stirring to make 18l. Finish and adjust pH to 4.40 with sulfuric acid and sodium hydroxide.

The processing was carried out at development 35 ° C., fixing 33 ° C., washing with water 20 ° C. and drying 50 ° C., and dry to dry was performed for 45 seconds.

[0131]

[Table 4]

From Table 4, it can be seen that even if the solid fine particle dispersion of the dye of the present invention is contained in the silver halide photographic light-sensitive material, it does not adversely affect the photographic characteristics such as sensitivity, fog and gamma. In addition, the sample according to the present invention had good coating properties without failure due to uneven coating. Furthermore, as a result of testing the raw storability of each sample, it was not different from the blank sample at all.

[0133]

Industrial Applicability According to the present invention, firstly, a solid fine particle dispersion of a dye which prevents the growth of microorganisms and has excellent storability with time can be provided. Secondly, it is possible to provide a silver halide photographic light-sensitive material containing a solid fine particle dispersion of a dye having an excellent coating film state.

Claims (2)

[Claims] 1. At least one of the compounds represented by the following general formulas (1) to (5) is 0.1 mg to 30 mg per 1 g of the dye, and at least one of the dyes represented by the following general formulas (I) to (VI). A solid fine particle dispersion of a dye, comprising one kind and at least one kind of anionic surfactant and / or nonionic surfactant and a hydrophilic colloid. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carbamoyl group, a thiocarbamoyl group, or a sulfamoyl group,
R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group,
It represents an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic group, and R ₂ and R ₃ may combine with each other to form an aromatic ring. ] [Chemical 2] [In the formula, R ₄ and R ₅ represent a hydrogen atom or an alkyl group. ] [Chemical 3] [In the formula, R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group,
It represents an aryloxycarbonyl group, an amino group or a carbamoyl group, and R ₈ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a carbamoyl group or a heterocyclic group. ] [Chemical 4] [Wherein R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom,
Represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group or a carbamoyl group, and R ₉ and R ₁₀ are bonded to each other to form a double bond. You may form. R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a carbamoyl group or a heterocyclic group. ] [Chemical 5] [In the formula, R ₁₄ is a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
It represents an amino group or a carbamoyl group, and l represents an integer of 1 to 5. ] [Chemical 6] [In the formula, A and A ′ may be the same or different,
Each represents an acidic nucleus, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, Q'represents a heterocyclic group,
X and Y, which may be the same or different, each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n represents 0, 1 or 2, and p represents 0 or 1. However, in the general formula (I)
The dyes represented by to (VI) have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. ] 2. A support having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer containing the solid fine particle dispersion of the dye according to claim 1. A characteristic silver halide photographic light-sensitive material.