JPS62265651A - Spectrally sensitized silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material ensuring high photosensitivity and contrast and causing little dye stain by incorporating a specified compound and a prescribed surface active compound into hydrophilic colloidal layers contg. a silver halide emulsion layer formed on a substrate. CONSTITUTION:A compound represented by the formula and a fluorinated surface active compound are incorporated into hydrophilic colloidal layers including a silver halide emulsion layer formed on a support. In the formula, Z is a group of nonmetallic atoms required to form an oxazole, benzoxazole or naphthoxazole ring, R<1> is alkyl, R<2> is alkoxycarbonylalkyl, hydroxyalkyl or other prescribed group, each of R<3> and R<4> is H, Cl, F, alkyl, alkoxy, alkylsulfonyl or sulfo and n=1,4. The compound represented by the formula is a merocyanine dye and the amount of the dye used is 10<-5>-2X10<-3>mol per 1mol silver halide. The amount of the surface active compound used is 10<-5>-10g, preferably 10<-4>-5X10<-1>g per 1g hydrophilic colloid.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic material that is spectrally enhanced by a novel merocyanine dye, and in particular has high sensitivity to green light and can produce halftone images with high contrast. The present invention relates to a silver halide photographic material that can be obtained even in relatively rapid development and has extremely little dye staining after processing.

Margins Below [Prior Art] It is well known that photographic images with extremely high contrast can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is about 0.5μ
Silver halide consisting of a silver chlorobromide or silver chloroiodide emulsion with fine grains of m or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 mol% or more. A method is known in which a high-contrast halftone dot image or line image is obtained by processing a photosensitive material with an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions.

Margin below This type of silver halide photosensitive material is known as a lithium-type silver halide photographic photosensitive material, and normally during the photolithography process, continuous gradation density changes of the original are converted into large and small areas proportional to this density. It is used to convert to a set of halftone dots with . Such conversion uses a lithium-type silver halide photographic light-sensitive material, images the original through a cross-line screen or a contact screen, and then processes the original with a very low concentration of sulfite ions and contains only a hydroquinone developing agent. A halftone image is formed by developing with a so-called Lith type developer. This lithium-type silver halide photographic light-sensitive material is produced using a conventional developer with a high concentration of sulfite ions.
For example, even if processed with a commercially available developing solution for photographic paper, the gamma is only 5 or 6, and fringes, which must be avoided in halftone dot formation, occur frequently. It is said that combination with mold developer is essential. Regarding this squirrel type developer, please refer to J.
Journal of the Franklin Institute (J, A, CYu)
le: J, Franklin In5t
itute), Volume 239, Page 221 (19
45), this is a developer solution containing essentially only hydroquinone as a developing agent and having a low concentration of sulfite ions, which serves as an antioxidant for the developing agent.

Such developers have poor shelf life and are susceptible to auto-oxidation, so in order for plate makers to consistently obtain high-quality halftone negative or halftone positive images, they must reduce the activity of the developer, which decreases over time. Although it is necessary to manage the developer to maintain a constant value, it is unavoidable that the operation becomes complicated.

Furthermore, in the lithographic development process, there are two major disadvantages: in addition to the above-mentioned developer management that keeps the activity constant, the processing speed is slow.

The trend in printing plate making in recent years has been to shorten the printing process and shorten the time, and there is an increasing demand for processing speed of plate making film.

For example, Japanese Patent Application No. 59-240147 uses a silver halide photographic light-sensitive material containing a tetrazolium salt as a technique for obtaining an extremely high contrast image suitable for plate making using a developer with high stability. A method is disclosed. This method allows the use of a stable developer with a high concentration of sulfite ions, and enables rapid processing with a development time of around 30 seconds and a drying time of 90 to 100 seconds, which was not possible with conventional lithography. be.

On the other hand, silver halide photographic materials for use in plate making are generally required to have so-called orthotype photosensitivity, which is photosensitivity in the green area.

Since a photosensitive silver halide emulsion alone has a narrow wavelength range of sensitivity, a spectral sensitizer is used for the purpose of expanding the wavelength range of sensitivity to longer wavelengths. For example, as a device that imparts sensitivity to green light,
No. 28, No. 40-392, No. 43-10251, No. 43-22884, British Patent No. 815.172, No. 9
No. 55.961, No. 955.912, No. 142.22
No. 8, U.S. Patent No. 1,942.854, U.S. Patent No. 1,950.
No. 876, No. 1,957,869, No. 2.238.2
No. 31, No. 2,521,705, No. 2,647.05
No. 9, Special Publication No. 43-2606, No. 44-3644,
No. 46-18106, No. 46-18108, No. 48
-15032, 49-33782, 54-34
No. 252, No. 58-52574, U.S. Patent No. 2.839
．． No. 403, No. 3,567.458, No. 3,625,
Examples include cyanine dyes and merocyanine dyes described in specifications such as No. 698.

[Problem that the invention seeks to solve]

These spectral sensitizers increase the sensitivity in a specific wavelength range, and at the same time have general properties such as (al) not being affected by other additives or affecting the effectiveness of the additives; (b) No change in photographic properties such as a decrease in sensitivity or increase in fog even after time has passed (C) Properties such as no dye staining after processing are required, but the above comparison When rapid development is performed, dye staining after processing increases, which is a major problem in practice.

In order to reduce dye staining, it is necessary to use a material that has little staining property against hydrophilic colloids such as gelatin, and which easily flows out into the processing solution.
A spectral sensitizer with high solubility may be used, and various compounds have been proposed in the past.

However, in many cases, spectral sensitizers have a large effect on the development effect that provides the extremely high contrast required for plate making, resulting in problems such as a decrease in contrast. It was difficult to directly apply the solution to silver halide photographic materials that undergo high contrast development.

The purpose of the present invention is to solve the above-mentioned problems, and to provide high photosensitivity, to obtain an extremely rich contrast through rapid processing using a normal developer with a high concentration of sulfite ions, and to obtain a high contrast after processing. An object of the present invention is to provide a silver halide photographic material with extremely little contamination.

The following margin [Means for solving the problem] As a result of various studies, the present inventors have developed a support and a hydrophilic colloid layer coated on the support, including at least one silver halide emulsion layer. The above-mentioned silver halide photographic material is characterized in that the hydrophilic colloid layer contains a compound represented by the general formula [I] and a fluorinated surface-active compound. I discovered that I could achieve my goal.

General formula CI) Z represents an atomic group necessary to complete an oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus, and these nuclei may have a substituent on a carbon atom. Specific examples of substituents include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), unsubstituted alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group,
butyl group, hexyl group, etc.), alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, propoxy group, butoxy group), hydroxy group, alkoxycarbonyl groups having 2 to 6 carbon atoms (e.g. methoxycarbonyl group, ethoxy carbonyl group, etc.), an alkylcarbonyloxy group having 2 to 5 carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), phenyl group, hydroxyphenyl group, and the like.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4.5-dimethyloxazole, 4-phenyloxazole, etc. as the oxazole nucleus; benzoxazole, 5-chlorobenzoxazole, etc. as the benzoxazole nucleus; 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6- Naphtho(1,2-
d) Nuclei such as oxazole, naphtho(2,1-d)oxazole, and naphtho(2,3-d)oxazole can be mentioned.

R1 represents an unsubstituted or substituted alkyl group.

Examples of substituents include hydroxy groups, sulfo groups, sulfonate groups, carboxy groups, halogen atoms (e.g. fluorine atoms, chlorine atoms), unsubstituted or substituted alkoxy groups having 1 to 4 carbon atoms (alkoxy groups further include sulfo groups, may be substituted with a hydroxy group), an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a sulfamoyl group, an unsubstituted or substituted carbamoyl group (an alkyl group having 1 to 4 carbon atoms) (including substituted carbamoyl groups), substituted phenyl groups (examples of substituents include sulfo groups, carboxy groups, hydroxy groups, etc.), vinyl groups, and the like.

Specific examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of substituted alkyl groups include 2-hydroxyethyl and 3-hydroxypropyl groups as hydroxyalkyl groups, and 2-sulfoethyl and 3-hydroxypropyl groups as sulfoalkyl groups.
-Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2
-chloro-3-sulfopropyl group, carboxyalkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, 2,2.2-1-lifluoroethyl group, 2-(3-sulfopropyloxy)ethyl group, 2-(2-hydroxyethoxy)ethyl group,
Ethoxycarbonylethyl group, methylsulfonylethyl group, 2-sulfamoylethyl group, 2-carbamoylethyl group, 2-N, N-
dimethylcarbamoylethyl group, phenethyl group, p
-Carboxyphenethyl group and sulfoaralkyl group include p-sulfophenethyl group, 0-sulfophenethyl group, p-hydroxyphenethyl group, allyl group, phenoxyethyl group, and the like.

R2 is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl group, or a substituent + CHt -)-;A or -+
CHz←O→CH2→→express. Here A is a nitrile group,
It represents an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamine group, or an alkoxy group having 1 to 8 carbon atoms, and n represents an integer value of 1 to 4.

Each of the above groups includes those having a substituent. For example, those in which the alkyl moiety of the above group is substituted with a halogen atom can also be preferably used. Examples of RZ include alkoxycarbonylalkyl groups in which each alkyl group is substituted with a halogen atom (e.g., methoxycarbonylfluoromethyl group, ethoxycarbonylfluoromethyl group, fluoroethoxycarbonylethyl group, etc.), hydroxyalkyl groups (e.g., 2-hydroxy Fluoroethyl group, 2-
Hydroxyfluoropropyl group, 3-hydroxyfluoropropyl! , 2.3-dihydroxyfluoropropyl group, etc.), hydroxyalkoxyalkyl group (e.g., hydroxymethoxyfluoromethyl group, 2-(2-hydroxyfluoroethoxy)ethyl group, 2-hydroxyfluoroethoxymethyl group, etc.), carbamoylalkyl group ( N
-alkyl-substituted, N + N-dialkyl-substituted, N-hydroxyalkyl-substituted, N-alkyl-N-hydroxyalkyl-substituted, N,N-di(hydroxyalkyl)-substituted substituted carbamoyl alkyl groups and cyclic 5- and 6-membered rings amine carbamoylalkyl group) (e.g. 2-carbamoylchloroethyl!, 2-N-(2-hydroxyethyl)carbamoylchloroethyl group, N-hydroxyfluoroethylcarbamoylmethyl group, N sN';
(2-hydroxyfluoroethyl)carbamoylmethyl group, 2-N,N-di(2-hydroxyethyl)carbamoylchloroethyl group, N,N-dimethylcarbamoylchloromethyl group, cerphorinocarbamoylchloromethyl group, piperidino carbamoylmethyl group, etc.), hydroxyphenyl group, hydroxyalkylphenyl group having 7 to 9 carbon atoms (e.g., p-(2-hydroxyfluoroethyl)phenyl group, m-(1-hydroxyfluoroethyl)phenyl group, etc.), or substituted Base +CH! −) −iA or +CHt +−o −(−CI(z−)−, %A
represents. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfamide group, an alkylsulfonylamino group, or a lower alkoxy group, and among these, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (for example, methylsulfonyl The sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms (for example, N-methylsulfonyl group, N-methylsulfonyl group, etc.).

N-dimethylsulfonylamino group, etc.), the alkylsulfonylamino group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms (for example, methylsulfonylamino group, etc.), and the lower alkoxy group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms. 1 to 4 alkoxy groups (eg, methoxy group, ethoxy group, etc.).

n represents an integer value of 1-4.

R3 and R4 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably one with 1 to 4 carbon atoms, such as a methyl group or an ethyl group), or an alkoxy group (preferably one with 1 to 4 carbon atoms). , for example, a methoxy group, an ethoxy group), an alkylsulfonic acid group, a sulfonic acid group, a chlorine atom, a fluorine atom, or a carboxy group.

Particularly preferred compounds of the above general formula [I] are those in which R1 represents a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a sulfo group or a carboxyl group and/or a hydroxyl group. Yes, specifically sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3-sulfo-2
-Hydroxypropyl group, etc.

Next, typical examples of the compound represented by the general formula CI) used in the present invention will be given, but it goes without saying that the compounds used in the present invention are not limited to these.

The following margins (exemplary compounds) (1) -3, CH3 (I) -4 (I)-5 (I)-6 (I)-70CH3 "CH!503K CH1 (t) -170CHi H3 (I)-18 CI )-20 (CHz) 3sOJa (I)-23 (I)-24 (+)-25 CI)-26 (I)-29 (I)-30 (I)-33 CHzSOJ The above general used in the present invention The compound represented by formula [I] is disclosed in Japanese Patent Publication Nos. 46-549 and 46-18105.
No. 46-18106, No. 46-18108, No. 47-4085, No. 58-52574, U.S. Patent 2
, No. 839,403, No. 3,384.486, No. 3,
No. 625,698, No. 3,480.439, No. 3,5
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 67゜458 and the like.

The merocyanif dye represented by the general formula CI) used in the present invention can be added and dispersed in a silver halide emulsion by various methods, such as conventionally known methods. For example, the method of adding by dispersing with a surfactant described in the specifications of JP-B No. 49-44895 and JP-A-50-11419;
No. 24, No. 53-102732, No. 53-10273
3, U.S. Patent No. 3.469,987, U.S. Patent No. 3.676
, a method of adding it as a dispersion with a hydrophilic substrate as described in the specification of No. 147, and a method of adding it as a solid solution as described in the specification of East German Patent No. 143.324. In addition, the merocyanine dye may be dissolved in a water-soluble solvent such as water, ethanol, methanol, acetone, n-propanol, fluorinated alcohol, pyridine, etc. alone or in a mixture thereof and added to the emulsion. It may be added at any time during the emulsion manufacturing process, but preferably during or after chemical ripening. The amount of the merocyanine dye used in the present invention is the amount for spectral sensitization of the silver halide emulsion, for example, 10 - s to 2 s per mole of silver halide.
X10-1 mol, preferably lXl0-' to 2X10-
'It's a mole.

Further, the merocyanine dye used in the present invention is, for example,
Special Publication No. 43-4933, No. 43-4936, No. 46
-18107, 46-1999, 47-111
No. 14, No. 48-1762, No. 48-38408,
Used in combination with other dyes disclosed in the specifications of U.S. Pat. No. 56-38937, U.S. Pat. No. 58-52574, U.S. Pat. This allows for supersensitization.

The fluorinated surfactant compound of the present invention may be any of the known surfactants that can be used in silver halide photographic light-sensitive materials, and compounds in which some of these surfactants are particularly substituted with fluorine atoms. It is.

Compounds classified as (a) to [10] below are particularly preferred, but are not limited to these.

The following general formula (,aj (b)(c,,)('d)(e)
It can be expressed as (f).

General formula (a) (F)n+ In the formula, R1! represents an alkyl group having 1 to 32 carbon atoms, such as a methyl group, ethyl group, propyl group, hexyl group, nonyl group, dodecyl group, hexadecyl group, etc., and these groups are substituted with at least one fluorine atom. has been done.

n represents an integer of 1 to 3, and nl represents an integer of O to 4.

General formula (b) General formula (C) In the formula, RI31 RI41 RI&l Rat and R11+ are each a linear or branched alkyl group having 1 to 32 carbon atoms, such as a methyl group, an ethyl group, a butyl group, an isobutyl group, It represents a pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, etc., but it may also be an alkyl group that forms the same group, and any of these groups is substituted with at least one fluorine atom. . Also R13. R14+ R11k+R17 and R11
Each of 1 may be an aryl group, such as a phenyl group or a naphthyl group. These aryl groups are substituted with at least one fluorine atom or a group substituted with at least one fluorine atom.

Furthermore, R+r and RI4 represent an acid group such as a carboxylad group, a sulfonate group or a phosphoric acid group.

General formula (d) In the formula, R2 represents a saturated or unsaturated linear or branched alkyl group having 1 to 32 carbon atoms. Examples of the saturated alkyl group include a methyl group, an ethyl group, a butyl group, and an isobutyl group. , hexyl group, dodecyl group, octadecyl group, etc., and unsaturated alkyl groups include, for example, allyl group, butenyl group, octenyl group, etc. These saturated and unsaturated alkyl groups are substituted with at least one fluorine atom. n2 and n represent integers of 1 to 3. Also n4
represents an integer from 0 to 6.

General formula (e) In the formula, Y represents a sulfur atom, a selenium atom, an oxygen atom, or an alkyl group having 1 to 3 carbon atoms, such as a methyl group or an ethyl group. ) in RI! represents an alkyl group having 1 to 32 carbon atoms substituted with at least one fluorine atom or an aryl group substituted with at least one fluorine atom (e.g., phenyl group, naphthyl group, etc.). Also, Z is 5
Represents an atomic group necessary to form a membered or 6-membered heterocycle, examples of which include thiazole ring, selenazole ring, oxazole ring, imidazole ring, pyrazole ring,
Examples include a triazole ring, a tetrazole ring, a pyrimidine ring, and a triazine ring.

The above heterocycle may further have a substituent such as an alkyl group or an aryl group, and these substituents may be substituted with a fluorine atom.

General formula (f) Rzz-e-CHz CHz O→1S 030 In the formula, represents a fluorinated alkyl group. n takes an integer value of 1-4.

Next, specific examples of the fluorinated surfactant compounds represented by the above general formulas (a) to (f) will be shown, but the compounds that can be used in the present invention are not limited to these.

(Exemplary compound) (,3) OF’.

■ (2o) ay.

0P H(CFz)icII□C11z -0-CHzCII
□O-SO.

11(CFz) a-CIIzCHg-0-CH□CH
zO-SoρuC! , El, Coo(, El (iso)
(Mhos S-OH-coocn,
(aFl, aFl,)3 B■ CH, -000CTl, CFlo, H.

C2-(Ukl, ULJL)G, I(, (nJa) Nap, E -OEi -Coo(II(, (OF,
OIP@)? Han! -coocR.

Nap, S - (HCOOC! H2-OF, OF, H
0H, -COOC1゜H,, (n) 37] Nap, 8 - (:H-0000H2(CF,
CFg )2 HCH,0OOC,H,, (isol edict) Nap, S -CHCOOCH, (CIF20F,
), T1CM, C00C,l'l,, (n)N
ap, S-(H-C00CH, (CF, l,
H0B, -C00CH, (CF, l, H In order to incorporate the fluorinated surfactant compound used in the present invention into a silver halide photographic light-sensitive material, a known surfactant used in a silver halide photographic light-sensitive material can be used. In other words, it can be contained in any of the silver halide emulsion layer, the hydrophilic colloid layer adjacent to the emulsion layer, or even the adjacent hydrophilic colloid layer via an intermediate layer.Preferably, it can be contained in the emulsion layer. It is to be contained in the upper hydrophilic colloid layer adjacent to the layer.For addition and dispersion, it may be added by being dissolved in a single or mixed solvent such as water, ethanol, tutanol, acetone, or fluorine alcohol. Although it may be added at any time during the emulsion manufacturing process, it is more preferable to add it to the coating preparation solution for the emulsion layer or protective film.

The amount of fluorinated surface-active compound added is between 10-5 and 10 grams per gram of hydrophilic colloid, preferably 10-
4-5 Xl0-' grams.

The silver halide used in the silver halide photographic light-sensitive material of the present invention can be used in any composition.

In addition, the average grain size of silver halide grains is 0.05 to 0.5μ.
It is preferable to use one in the range of m, and 0.10 to
More preferably 0.40 μm.

Regarding the monodispersity of the silver halide emulsion used in the present invention, the value is preferably 5 to 25, more preferably 8 to 2.
The grain size of the silver halide grains used in the present invention is conveniently expressed by the principal dimension of cubic grains, and the monodispersity S is calculated by averaging the standard deviation of the grain size as shown in the following formula (1). It is expressed as a value obtained by dividing the value divided by the particle size Y and multiplying it by 100.

Further, as the silver halide that can be used in the present invention, for example, a type having a multilayer laminated structure of at least two layers can be used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or vice versa, silver bromide in the core and silver chloride in the shell. It can be contained within mol%.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparing the emulsion coating solution.

In this case, the rhodium salt may be a double salt as well as a simple salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The amount of rhodium salt added can be freely changed depending on the required sensitivity and gradation, but it ranges from 10-1 mol to 1 mol per mol of silver.
A range of 0-6 moles is particularly useful.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts are often used for high-intensity body parts purposes and can be preferably used in the range of 10-' moles to 10-6 moles per mole.

The silver halide used in the present invention has the general formula (1)
In addition to spectral sensitization using the compounds described above, sensitization can be performed using various chemical sensitizers. Examples of sensitizers include activated gelatin, sulfuric acid sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction Sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooleite, potassium aurothiocyanate, potassium chlorooleate,
2-Aurosulfobenzothiazole methyl chloride,
Various noble metal sensitizers represented by ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc. can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The spectrally sensitized silver halide and the compound represented by the general formula (II) used in the present invention are made to exist in the hydrophilic colloid layer, and hydrophilic colloids particularly advantageously used in the present invention include: Gelatin is preferred, and hydrophilic colloids other than gelatin include, for example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, and gelatin derivatives. , for example, phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin, as described in U.S. Pat. No. 2,614,928, U.S. Pat. , No. 548.520, No. 2.831, 7
Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in the specifications of No. 67. I can,
These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Representative examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

The light-sensitive material according to the present invention contains a compound represented by the general formula (II) of the present invention in a hydrophilic colloid layer including at least one silver halide emulsion layer on a support as described above, for example. However, a hydrophilic colloid layer having an appropriate thickness, preferably 0.1 to 10 μm, particularly preferably 0.8 to 2 μm, is coated as a protective layer on the silver halide emulsion layer. It is particularly preferable to have.

The silver halide emulsion layer and wood-philic colloid layer used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, and ultraviolet absorbers, as necessary. , antistaining agents, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed adjusters, matting agents, etc., which may impair the effects of the present invention. It can be used within a certain range.

Among the various additives mentioned above, those that can be particularly preferably used in the present invention include thickeners and plasticizers, such as those described in U.S. Pat.
Publication No. 39, West German Application Publication No. 1, 904, 604
specification, JP-A No. 48-63715, JP-A No. 45-1
Publication No. 5462, Belgian Patent No. 762,833,
US Patent No. 3.767.410, Belgian Patent No. 5
Substances described in the specifications of No. 58.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl Examples of various hardening agents and ultraviolet absorbers such as sulfone type, isocyanate type, nistil sulfonate type, carbodiimide type, mucochloric acid type, acyloyl type, etc., include U.S. Patent No. 3,253,921 and British Patent No. 1. .309.34
Compounds described in each specification etc. of No. 9, especially 2-(
2'-Hydroxy-5-tertiary butylphenyl)pen'/
'l-Rya7'-l, 2-(2-hydroxy-3,
5-di-tertiary butylphenyl)hencytriazole, 2
- (2-hydroxy-3-.

tertiary butyl-5-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3゜5-di-3
butylphenyl)-5-chlorobenzotriazole, etc., and as dyes, U.S. Pat.
, 072,908, Narrow Patent No. 107.990, U.S. Patent No. 3,048,487, U.S. Patent No. 515,9
Compounds described in various specifications such as No. 88 can be used, and these compounds may be contained in a protective layer, an emulsion layer, an intermediate layer, or the like. Further, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent No. 548,532; No. 1,221,980, U.S. Patent No. 2.992.101
No. 2.956.884, Buddhist Temple Patent No. 1,395
, No. 544, Japanese Patent Publication No. 48-43125, etc. are preferred, especially compounds with a 0.5 to 20μ
Examples include silica gel having a particle size of m, and polymethyl methacrylate polymer having a particle size of 0.5 to 20 μm.

The silver halide photographic light-sensitive material containing the compound of general formula (II) of the present invention in the silver halide emulsion layer and/or other hydrophilic colloid layer can be used in the presence of a compound represented by the following general formula (III). It is preferable to develop with.

[In the formula, R31 is a 5- or 6-position nitro group, R3
□ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion. ] As a specific compound represented by general formula (III), 5-
Examples include nitroindazole and 6-nitrointasole, but the present invention is not limited thereto in any way.

The compound represented by the general formula (I It may be added to the developer or may be added as is.

The compound represented by general formula (III) is contained in a concentration range of preferably about 1 mg to 1,000 mg, more preferably about 5 Q mg to 300 mg, per developer solution 11.

Examples of the developing agent for the silver halide photographic light-sensitive material of the present invention, particularly for the black-and-white photographic light-sensitive material, include the following. This developing agent can be used together with the compound represented by the above-mentioned general formula (In).

) 10 + CI = CH + iOH type development Main developing agents include hydroquinone, as well as catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2,5-di-
p-Phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4-(2-hydroxy Benzoyl) pyrogallol, sodium ascorbic acid, etc.

In addition, typical examples of HO÷CH=CH-+TNJ type developers include ortho and rose aminophenols or aminopyrazolones, including 4-aminophenol, 2-aminophenol,
Amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, 2,4 -cyamylsorcinol, 2,4.6-1-riaminophenol,
N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc.''.

Furthermore, examples of H2N + C= C-+TNHz type developers include 4-amino-2-methyl-N, N-diethylaniline, 2.4-diamino-NN-diethylaniline, N-(4-amino-3 -methylphenyl)-morpholine, p-phenylenediamine, 4-amino-N,N-
Dimethyl-3-hydroxyaniline, N, N, N, N-
Tetramethylparaphenylenediamine, 4-amino-N
-ethyl-N-(β-hydroxyethyl)-aniline,
4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-
(β-methoxyethyl)-3-methyl-aniline, 4-
Amino-3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)-aniline, 4-amino-N-butyl-N-n-sulfobutylaniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl,
1.2°3.4-Tetrahydroquinone harm h<ab.

Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and l-phenyl-4-dimethyl-3-pyrazolidone. -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Pyrazolidones, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2
-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 5-aminouracil and the like.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition) pages 291-334 and Journal of the American Chemical Society (Journal of the A+weri)
Developers such as those described in vol. 73, p. 3.100 (1951) of Can Chemical 5ociety) can be effectively used in the silver halide photographic light-sensitive material of the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as potassium sulfite or ammonium sulfite is used as a preservative in the developer used for processing the photosensitive material of the present invention, the effects of the present invention will not be impaired, and the effects of the present invention will not be impaired. This can be cited as one feature.

Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting 9H with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as bromkali, organic development inhibitors such as benzotriazole, and ethylenediaminetetraacetic acid, etc. Metal ion scavenger, development accelerator such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, sodium alkyl 71J-rusulfonate, natural saponin, surfactant such as saccharide or alkyl ester of the above compound, glutaraldehyde, formalin. , a hardening agent such as glyoxal, an ionic strength adjusting agent such as sodium sulfate, etc. may be optionally added.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the alkanolamines mentioned above include triethanolamine jetanolamine, ethanolamine trimethylamine 2-diethylamino-1-ethanol 2-methylamino-1-ethanol 3-dimethylamino-1-propanediol 3-diethylamino-1-propanol 5-Amino-1-pentanoldiethylamine methylamine triethylamine dipropylamine di-isopropylamine 3.3'-diaminodipropylamine 3-dimethylamino-1-propatolhydantoic acid allylamine ethylamine dimethylamine ethylenediamine 2-dimethylaminoethanol 2 -ethylaminoethanol 2-(2-aminoethylamino)ethanoltetramethylammonium acetatecholinecholine chloridehydroxylamine sulfate 2-((2-aminoethylamino)-ethylaminetwoethanolaminoguanidine sulfate 6-aminohexanoic acid 3-amino- 1-Propatol 1-dimethylamino-2-Propatol 2-Hydroxy-4-thiadodecyltrimethylammonium (pta) Pyridine Glycine O-Amine Benzoic Acid Polyethyleneimine L-(+)-Cystine Hydrochloride Benzylamine 2-Amino- 1-ethanol 4-amino-I-pukunor 3-(dimethylamino)-1,2-propanediol 3-morpholino-1,2-propanediol 1,4-piperazine bis(ethanesulfonic acid) 3-piperidino-1
, 2-propanediol, N-piperidine ethanol, and the like.

In addition, the above glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g, preferably 20 to 200 g per 11 of the developer.

These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention can be developed with a developer containing the above-mentioned development inhibitor, thereby obtaining photosensitive characteristics with extremely excellent storage stability. ``p of the developer having the above composition
The H value is 9 to 12, but the pH value is preferably in the range of 10 to 11 from the viewpoint of storage stability and photographic properties.

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably around 30°C, and the development time is generally completed within 3 minutes.
Particularly preferably within 40 seconds often brings about good results. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called early field image processing such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕

A silver chlorobromide emulsion was prepared using the following solutions A, B, and C.

Solution A> Ossein gelatin 17 g Polyisopropylene-polyethylene oxydisuccinate sodium salt 5...110% ethanol solution Distilled water
1280 cc Solution B> Silver nitrate 170 g Distilled water 410 ml Solution C>
.

Sodium chloride 40.9 g Potassium bromide 35.7 g Polyisopropyleneoxydisuccinate sodium salt 10
% ethanol solution 3ml ossein gelatin
11 g distilled water
After keeping 401ml of solution A at 40℃, the EAg value was 16.
Sodium chloride was added so that the concentration was 0 mv.

Next, solutions B and C were added by a double jet method using the mixing agitator described in JP-A-57-92523 and JP-A-57-92524.

As shown in Table 1, addition was carried out by gradually increasing the addition flow rate over a total addition time of 80 minutes while keeping the EAg constant.

EAg value is 3 ml 5 minutes after starting addition from 160a+v
EAg value 120 using l/l sodium chloride aqueous solution
mv and maintained this value thereafter until the completion of mixing.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol/l aqueous sodium chloride solution.

Table 1: For the measurement of EAg values, a metal silver electrode and a double junction silane type saturated Ag/Agcz reference electrode were used. ).

Further, a variable flow rate roller tube metering pump was used to add solutions B and C.

Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system.

Also, during the addition, the pH value of the system was kept constant at 3.0.
% nitric acid aqueous solution.

After addition of solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then desalted and washed with water using a conventional method. After that, 600mj of an aqueous solution of ossein gelatin was added. (containing 30 g of ossein gelatin) was added and dispersed by stirring at 55° C. for 30 minutes, and the volume was adjusted to 750 cc.

Next, this emulsion was subjected to sulfur-containing sensitization, and 6-methyl-4-hydroxy-1+ 3+ 3a was used as a stabilizer.

7-Chitrazaindene was added. The emulsion was divided and the compound of general formula (1) according to the present invention was added to the emulsion as shown in Table 2. Or for comparison, the sensitizing dye shown below ((
1) -(a) to (4>>3 Xl0-'mol 1
After adding moles of Ag as shown in Table 2, an additional 600+wg/A of sodium n-dodecylbenzenesulfonate was added.
g 1 mol, 2.3.5-) diphenyltetrazolium chloride 60 g/Ag 1 mol, styrene/7-maleic acid copolymer 2 g/Ag 1 mol were added, and Ag 3.5 g/m2 and gelatin were placed on a polyethylene terephthalate film. It was applied in an amount of 2.0 g/m2. At this time, a fluorinated surfactant compound as shown in Table 2 and comparative surfactant compounds ((a) to (C)) were added so that the amount of gelatin was 1.0 g/rrr, and a hardening agent was added. A dura protective layer containing formalin 25a+g/rrl was applied in multiple layers.

,,1. +NoU-/ Comparative sensitizing dye (I) -(e) Comparative sensitizing dye [1]-(a) [N-(b) (1)-(C) Comparative externally active compound (■) -(a ) -(b) -(c) -(d) -(e) Take three pieces of each of the obtained samples, apply a stepwise exposure to one piece using a tungsten light using a sensitometer and apply an optical wedge to the other piece, and One piece includes contact screen No. 2 (150L) manufactured by Dainippon Screen Manufacturing Co., Ltd.
) was used to expose the shaded areas to xenon light. Also,
The remaining piece was subjected to the following processing without being exposed to light.

The above sample piece was processed in an automatic developing machine with a developing tank capacity 1401 using a developer having the following formulation and a commercially available fixer.

[Development processing conditions]

(Process) (Temperature) (Time) Development 28℃
30 seconds fixing 28℃ 20 seconds washing 20℃ 20 seconds drying 40℃ 20 seconds [Developer composition] (Composition A) (Composition) Pure water 500mA when using developer! The above composition A was dissolved in the order of composition A and composition II was prepared and used.

For developed samples subjected to wedge exposure, draw a photographic characteristic curve and calculate the sensitivity at an optical density of 2.5 for sample N.
The relative value is calculated based on 001, and gamma is an optical density of 1.
tan of the straight section from 0 to 2.5.

The value was shown.

The quality of the formed mesh (dot quality) for M4 images taken using xenon light and a printing plate-making camera.
was evaluated.

For dot quality, for so-called 50% dots where the area of the halftone area and the clear area are equal, the state of the fringe (blur) that occurs around the halftone dot is visually judged, and the smaller fringe is evaluated as 5.
Evaluation was made on a five-point scale.

That is, "5" is excellent, and "1" is extremely bad. If the 50% dot quality is below @3'', this is generally unacceptable.

In addition, for samples processed without exposure, 4 films were stacked and the residual color of the film was visually evaluated and evaluated on a 5-point scale, with "5" being colorless and "1°" being a strong orange residual color. Indicated.

For general plate making, residual color below "3" is at a level that is considered a major drawback.

These results are shown in Table 3.

7. 2.) - The following margin: As shown in Table 3, the compound is color sensitized by the sensitizing dye represented by the general formula (■) according to the present invention and contains the compound represented by the general formula (■). The sample (rh+-11) has a relative sensitivity of 100-125 and the comparative sample (i'h i 2-1
8.80 or less), and the gamma is extremely strong at 16-20, and both the dot quality rank and residual color rank are superior to the comparative samples, indicating that the sample has less residual color. I understand.

〔Effect of the invention〕

As mentioned above, the silver halide photographic material of the present invention includes:
It has the advantage that an extremely high contrast can be obtained by rapid processing using a normal developer having high photosensitivity and a high sulfite ion concentration, and there is extremely little dye staining after processing.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Takatsuki Hirate 3 Sales Nail It Seisho (
1. Indication of the incident 1986 Patent Application No. 109014 2. Name of the invention Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent address: 506 Dia Palace Niban-cho, 11-9 Niban-cho, Chiyoda-ku, Tokyo, 102 FAX (03), 221-19245, Date of amendment order Vol. 6, Subject of amendment: 1. Detailed explanation of the invention in the specification.

7. Contents of the amendment As shown in the attached sheet 2. −? -ρ (1) “Sulfo
``amide group,'' is corrected to ``sulfamoyl group,''

(2) In the same page 2, lines 14-15, "alkylsulfonyl group" is corrected as "sulfoalkyl group."

(3) On page 14, line 14, "sulfonamide group" is corrected to "sulfamoyl group."

(4) Doshin page 16, lines 13-14 and doshin line 18-
"Sulboamide group" in line 19 and lines 19 to 20 of the same page are respectively corrected to "sulfamoyl group."

(5) On page 16, line 20, "N-methylsulfamide group" is corrected to "N-methylsulfamoyl group."

(6) rN on page 16, line 20 to page 17, line 1.

"N-dimethylsulfonamide group" is corrected to "rN,N-dimethylsulfamoyl group".

(7) On page 17, lines 12 and 13, "alkylsulfonic acid group" is corrected to "sulfoalkyl group."

(8) On page 17, line 13, "sulfonic acid group" is corrected to "sulfo group."

(9) The structural formula of r (I)-(a)j on page 72 of the same is corrected as follows.

that's all

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having a support and a hydrophilic colloid layer coated on the support and including at least one silver halide emulsion layer, wherein the hydrophilic colloid layer contains the following: A silver halide photographic material comprising a compound represented by the general formula [I] and a fluorinated surface-active compound. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z represents a group of nonmetallic atoms necessary to form an oxazole nucleus, benzoxazole nucleus, or naphthoxazole nucleus. R^1 represents an unsubstituted or substituted alkyl group. R^2 is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group,
Represents a carbamoyl alkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl group, or a substituent -(CH_2)-nA or -(CH_2)-_nO-(CH_2)-nA. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfamide group, an alkylsulfonylamino group, or an alkoxy group, and n represents an integer value of 1 to 4. R^3 and R^4 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylsulfonyl group, a sulfo group, a chlorine atom, a fluorine atom, or a carboxy group. ]