JPH06148776A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material improved in high contrast and prevented from extinction variation and fogging during high temp. and high humidity aging by incorporating the tetrazolium compd. having a reactive substd. group in a silver halide photosensitive emulsion layer. CONSTITUTION:The silver halide photographic sensitive layer has at least one silver halide photosensitive emulsion layer. In the silver halide photographic sensitive layer, the tetrazolium compd. having the reactive substd. group is incorporated. The tetrazolium compd. having the reactive substd. group is the compd. in which the tetrazolium compd. combines org. chemically with the reactive substd. group directly or through a binding group between both substd. part. The example of the substd. group is alkyl, hydroxyl, alkoxy group, etc. Then the tetrazolium compd. having the reactive substd. group is added to a AgX emulsion, after being adsorbed the tetrazolium compd. on the surface of AgX particles, the reactive substd. group is allowed to react with the functional group such as gelatin, and is binded by covalent bonding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-contrast silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved storage stability.

[0002]

2. Description of the Related Art In a photographic plate making process using a silver halide photographic light-sensitive material, a continuous tone original is converted into a halftone dot image, that is, a continuous tone density change has an area proportional to the density. It includes a step of converting the halftone image into a set of halftone dots and a step of converting the halftone image obtained in the step into a halftone image having better sharpness, that is, a returning step.

It is essential that the light-sensitive materials used in these processes have high contrast in order to obtain good halftone dot quality.

As a method for obtaining such characteristics, a light-sensitive material comprising a silver chlorobromide emulsion having a comparatively fine particle size, a narrow particle size distribution and a high silver chloride content has been developed with an alkali hydroquinone having a very low sulfite ion concentration. A method of processing with a liquid, a so-called lith development method, is known.

However, when this method is used, the concentration of sulfite ion in the developing solution is low, so that the preservability is extremely poor, and since the hydroquinone simple substance is used, the developing rate is slow and rapid processing cannot be carried out. It was

Therefore, a high contrast is obtained by treatment with a so-called PQ type or MQ type developer containing a super-additive developing agent having good preservability and capable of rapid processing, and containing a relatively high concentration of sulfite. Development of a new photosensitive material to be obtained is desired.

Regarding the novel light-sensitive material,
Japanese Patent Publication No. 59-17825, No. 59-18818, No. 59-17819,
59-17820, 59-17821, 59-17826, 59
No. 17822 discloses a silver halide photographic light-sensitive material containing a tetrazolium compound. The method of processing a light-sensitive material containing these tetrazolium compounds with a super-additive developer to obtain a silver image having a high contrast can be said to be an epoch-making technology in comparison with the conventional technology. Is becoming mainstream. However, if the gradation of a silver halide photographic light-sensitive material is kept extremely high and the sensitivity is made high, the storage stability under high temperature and high humidity is significantly deteriorated, and particularly, the sensitivity is lowered and the fog is generated. There are some drawbacks.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which has a high contrast and which is improved in desensitization fluctuation and fog with time under high temperature and high humidity.

[0009]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and tetrazolium having a reactive substituent in the silver halide emulsion layer. It is achieved by a silver halide photographic light-sensitive material characterized by containing a compound.

The present invention will be specifically described below.

A fog inhibitor is generally used to prevent fog during storage over time, but the sensitivity is reduced when the fog inhibitor is used. However, according to the present invention, it is possible to suppress fog without deterioration in sensitivity even after storage with time.

The tetrazolium compound having a reactive substituent in the present invention refers to a compound in which a tetrazolium compound and a reactive substituent are chemically bonded to each other directly or by a linking group, and is represented by the general formula Is represented as follows.

Tetrazolium compound- (L-reactive substituent) x Here, L represents a linking group, and x represents an integer of 1 to 3.

The tetrazolium compound mentioned above refers to a compound having a conventionally known substituted or unsubstituted phenyl group at the 2, 3, and 5 positions of the tetrazolium compound.

Examples of preferred substituents include alkyl groups
(E.g. methyl, ethyl, cyclopropyl, propyl,
Isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino group, acylamino group (eg acetylamino), hydroxyl group, alkoxy group (eg methoxy, ethoxy, propoxy, butoxy, pentoxy etc.), acyloxy group (eg acetyloxy) ), A halogen atom (for example, fluorine, chlorine, bromine, etc.), a carbamoyl group, an acylthio group (for example, acetylthio), an alkoxycarbonyl group (for example, ethoxycarbonyl),
Examples thereof include groups such as a carboxyl group, an acyl group (eg acetyl), a cyano group, a nitro group, a mercapto group, a sulfoxy group and an aminosulfoxy group.

The linking group represents a divalent linking group having 30 or less carbon atoms. The divalent linking group is alkylene, arylene,
_{Alkenylene, -SO 2 -, - SO -} , - O -, - S -, - CO -, - NR- (. R is representing a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group), a heterocyclic It represents a divalent group (for example, general formula [a]) alone or in combination.

[0017]

[Chemical 1]

The reactive substituent refers to a substituent which reacts with a functional group such as gelatin or latex polymer to form a covalent bond, and is a reactive group contained in a hardening agent for gelatin or a characteristic group by Steiger et al. Examples thereof include reactive groups described in JP-A-51-117619. For more information on these,
See below, and THJames Theory of the Photographic Process, 4th Edition, Macmillan Publishing, New York (1977).
), Chapter 2, Section III and AG Ward.and.A.Courts, The
Science and Technology of Gelation, Chapter 7, Academic Press New York (1977)
Can be referred to. More specifically, the reactive substituent is represented by an aldehyde group, a protected aldehyde group, an acid anhydride group, an acid halide group, a diketone group, an active ester group, an active halide group, an active olefin group, an isocyanate group, and an isocyanate group. It is a carboxyl group activated by an isocyanate group, an epoxy group, an aziridine group, a dioxolane group, an alkanesaltone group, a carboxyl azide group, an N-carbamoyl group, an isoxazolium base, an aromatic amino acid group, and a carbodiimide. Preferably, an aldehyde group, an acid anhydride group, an acid halide group, a diketone group, an active halide group, an active olefin group, an epoxy group, an aziridine group, an alkanesultone group, a carboxyazide group, a carboxyl group activated by carbodiimide. , An aziridene group, and a carboxyl azide group.

The reactive group may have two or more reactive groups such as a hard contrast agent, and it is more preferable.

Even if one of the reactive groups causes an ineffective reaction, the effect of the present invention can be achieved if the remaining reactive groups cause an effective reaction. Specific examples of the reactive substituents including the linking group L will be described below. L ₁ represents a part of the linking group. * Indicates a tetrazolium part. R _{1 and} R ₂ represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. X represents a halogen atom, and depending on the purpose, F, Cl,
A preferred atom can be selected from Br and I.

[0021]

[Chemical 2]

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

Specific examples of the carbodiimide include N, N'-dicyclohexylcarbodiimide and 1-ethyl.
Examples thereof include -3- (3-dimethylaminopropyl) carbodiimide, 1-benzyl-3- (3-dimethylaminopropyl) carbodiimide and the like.

In addition, as a method for activating the carboxyl group of the tetrazolium compound, a method using a condensation reagent such as N-ethyl-5-phenylisoxazolium 3'-sulfonate, pentachlorophenylchloroacetate,
The active ester method using p-nitrophenyl trifluoroacetate and p-nitrophenyl chloroacetate can be mentioned.

Next, specific examples of compounds will be shown.

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

The tetrazolium compound having the reactive group is added to the AgX emulsion, and the tetrazolium compound part is A.
After being adsorbed on the surface of the gX particles, the reactive group chemically reacts with a sensitive group such as gelatin and covalently bonds with gelatin and the like.
The chemical reaction is preferably completed before the product is shipped.
That is, the reaction is preferably 20% or more, more preferably 60% or more.
% Or more, more preferably 80% or more, is preferably completed. The binding reaction mainly proceeds during coating and drying and the subsequent heat treatment as in the case of the conventional hardener. The reaction is accelerated by the effect of increasing the gelatin concentration by drying (that is, the effect of increasing the functional group concentration) and the heat treatment after drying. Regarding the conditions at the time of the binding reaction, the hardening conditions with a conventional hardening agent can be referred to. That is, normally
The AgX emulsion is coated, the coated emulsion is gelled at 0 to 30 ° C, and dried at a relative humidity of 30 to 80% and a temperature of 15 to 40 ° C. Next, it is usually heated at 35 to 55 ° C and relative humidity of 80 to 100% or 100%, or after winding the coated film, it is sealed and heated at 35 to 55 ° C for 1 to 100 hours, Promotes the dura reaction. Also in the case of the present invention, the binding reaction can be promoted according to this.

The length of the connecting portion connecting the tetrazolium compound and the reactive group is preferably 0 to 100, more preferably 1 to 50 angstroms, and further preferably 4
You can choose from ~ 5 Å. When the length of L is short, the reactive substituent can react only with the functional group of gelatin near the surface of the AgX particles, but when L is long, it can react with the functional group of gelatin farther away. However, if L is too long, it becomes easy to desorb from the AgX particles.

It is also preferable to use a mixture of tetrazolium compounds having different L lengths. This is because the AgX particle surface can react with the functional groups of gelatin at various positions.

Examples of gelatin include gelatin and gelatin derivatives. More specifically, in addition to alkali-processed gelatin, acid-processed gelatin, derivative gelatin such as phthalated gelatin, low molecular weight gelatin (molecular weight of 2000-
100,000, oxygen-decomposed gelatin, acid / alkali hydrolyzed gelatin, pyrolyzed gelatin) Gelatin having a methionine content of 50 μmol or less, and oxidatively treated gelatin, or a mixture of two or more thereof. it can. As the derivative gelatin, gelatin is reacted with a compound such as acid halide, acid anhydride, isocyanates, bromoacetic acid, alkanesartones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds. What can be obtained is mentioned.

However, in the present invention, the reactive substituent bonded to the tetrazolium compound reacts with the functional group of gelatin to form a covalent bond, so that the derivative gelatin in which the functional group of gelatin is blocked is not preferable. This is because the reaction proceeds more rapidly when the number of functional groups that can be bonded is sufficient.When the functional group is -COOH, glutamine and asparagine are converted to glutamic acid or aspartic acid, which is an alkali-treated gelatin. More preferable. Further, gelatin in which arginine is converted to ornithine when the functional group is —NH ₂ is more preferable. In these cases, gelatin in which 30% or more, preferably 60% or more, and more preferably 90% or more of the —CONH ₂ group is converted to —COOH is more preferable. Further, gelatin in which 20% or more of arginine is converted into ornithine, preferably 40% or more, more preferably 80% or more, is more preferable. In these cases, the molecular weight of gelatin is preferably that of conventional photographic gelatin, and gelatin having an average molecular weight of 8 × 10 ^{4 to} 1.5 × 10 ⁵ is used.

The functional group of gelatin as used herein means an amino group, a carboxyl group and a hydroxyl group.

When -COOH is used as the functional group, it is more preferable to use gelatin in which the functional group is activated by allowing carbodiimide to act on the -COOH.

Regarding this, the description in JP-A-2-305876 can be referred to.

The hardening reaction with a hardening agent can be carried out at the time of the binding reaction in the conventional manner.

The silver halide used in the silver halide photographic light-sensitive material of the present invention is silver chlorobromide and has a silver chloride content of 50 mol% or more. The average grain size of silver halide grains is 0.10 μm
~ 0.50μm is preferable, (standard deviation of particle size) / (average particle size)
It is more preferable that the coefficient of variation represented by × 100 is 15% or less and the particle size distribution is narrow. Various kinds of sensitizers, sensitizing dyes, stabilizers and the like can be used in the silver halide used in the present invention. As the binder used in the present invention, those known in the photographic industry can be used, and the hydrophilic colloid which is particularly advantageously used is gelatin. These hydrophilic colloids can also be applied to layers containing no silver halide, such as antihalation layers, protective layers and intermediate layers. As the support used in the present invention, various supports used in the photosensitive material industry such as polyester film can be used. The light-sensitive material of the present invention is a protective layer having an appropriate film thickness, that is, preferably 0.1 to 10 μm, particularly preferably 0.8 to
A 2 μm gelatin protective layer is preferably applied.
In the hydrophilic colloid layer used in the present invention, if necessary, various photographic additives such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, antistain agents, pH adjusters. It is possible to use an antioxidant, an antistatic agent, a thickener, a graininess improver, a dye, a moldant, a whitening agent, a developing speed adjusting agent, a matting agent, etc. within a range in which the effect of the present invention is not impaired. it can. Examples of the developing agent used for developing the silver halide photographic light-sensitive material of the present invention include:
The Theory of the Photogra by H. James, 4th Edition
PhicPeocess, Fourth Edition) 291-334 and Journal of THeAmerican Chemical Soc-iety 73
Vol. 3, pp. 3,100 (1951), the developers can be effectively used in the present invention. These developers may be used alone or in combination of two or more kinds, but it is preferable to use two or more kinds in combination. Further, even if a sulfite such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the light-sensitive material of the present invention, the effect of the present invention is not impaired, and There are two characteristics. Further, hydroxylamine or a hydrazide compound may be used as a preservative. In addition, it is necessary to adjust the pH with a caustic alkali, an alkali carbonate, an amine or the like as used in a general black and white developer and to have a buffer function, and an inorganic development inhibitor such as potassium bromide and an organic development inhibitor such as benzotriazole, ethylenediamine. Metal ion scavengers such as tetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, sodium alkylaryl sulfonate, natural saponins, surfactants such as sugars or alkyl ester of the above compounds, glutar It is optional to add a hardening agent such as aldehyde, formalin and glyoxal, and an ionic strength adjusting agent such as sodium sulfate. The developer used for developing the light-sensitive material of the present invention may contain alkanolamines and glycols as organic solvents. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, and the like, and triethanolamine is preferably used. The preferred amount of these alkanolamines used is 5 to 500 g per liter of the developer,
More preferably, it is 20 to 200 g.

The silver halide photographic light-sensitive material of the present invention can be processed by development using the above-mentioned developing solution to obtain a light-sensitive material having extremely excellent storage stability. The pH value of the developer having the above composition is preferably 9 to 13, but the pH value is preferably in the range of 10 to 12 from the viewpoint of stability and photographic characteristics.

[0045]

EXAMPLES The present invention will be described in more detail by showing specific examples below.

Example 1 65 mol% of silver chloride by the control double jet method,
A silver halide emulsion having a halide composition of 35 mol% silver bromide and a grain size of 0.24 μm was prepared. After adding an appropriate amount of chloroauric acid and hypo to the obtained emulsion and changing the chemical ripening time to several points to obtain the maximum sensitivity, potassium bromide, sensitizing dye A and sensitizing dye B were halogenated respectively. 50 per mol of silver halide
After sensitizing by adding mg, 300mg, 100mg, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 500 mg per mol of silver halide. 1 of the obtained emulsion
Divide into 2 and add the tetrazolium compound having a reactive group of the present invention as shown in Table 1, and further add sodium p-dodecylbenzenesulfonate to 10 m per mol of silver halide.
g, styrene-maleic acid copolymer 20 mg, styrene-butyl acrylate-acrylic acid copolymer latex (average particle size of about 0.25 μm) After adding 0.2 g / m ² , the amount of Ag is 3.5 g / m
^{2. The} amount of gelatin was 2.0 g / m ² and coated on the polyethylene terephthalate film base having the undercoat described in Example 1 of JP-A-59-19941. At that time, gelatin amount 1.0
As spreading agents to be g / m ^2, bis (2-ethylhexyl) sulfosuccinate 10 mg / m ^2, matting agent (average particle size 4 [mu] m), formalin 25 mg / m ² more as a hardening agent
After the simultaneous coating of a protective layer containing the above, a backing layer having the following composition and a backing protective layer were coated on the opposite side of the film base and dried to obtain a sample.

[0047]

[Chemical 12]

(Backing layer composition)

[0049]

[Chemical 13]

Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² (backing protective layer) Gelatin 1 g / m ² Matting agent: Polymethylmethacrylate 15 mg / m ^{2 with an} average particle size of 3.0 to 5.0 μm Agent 10 mg / m ² Hardener: Glyoxal 25 mg / m ² The following high temperature and high humidity test was performed using the sample obtained as described above.

(High humidity, high humidity test)
After leaving it at 50% RH for 3 days, it was split in two, one for another 3 days under the same conditions, and the other for 3 days under the conditions of 40 ° C. and 80% RH.

The above sample was exposed with a tungsten light source through a step wedge, and then processed with a developing solution and a fixing solution having the following compositions under the following processing conditions.

The relative sensitivity indicates the amount of exposure that gives a density of 1.0, and is shown as a relative value with the comparative sample as 100. Contrast was expressed as the slope of the sensitometric curve giving a density of 0.1 to 1.0. The higher the value, the higher the contrast. Fog is represented by the fog density itself.

[0054] <Developer formulation> (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to make the pH of the used solution 10.4 Potassium bromide 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) ) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 700 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was made up to 1 liter. <Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% w / w aqueous solution) 13.6ml (Composition B) Pure water (ion exchanged water) 17ml Sulfuric acid (50% w / w aqueous solution) 4.7g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) 26.5g When using fixer The above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 l and used. The pH of this fixer is approximately
It was 4.3. The results are shown in Table 1.

[0055]

[Table 1]

From the results shown in Table 1, it can be seen that the samples of the present invention are excellent in high contrast even when stored under high temperature and high humidity, with little fluctuation in sensitivity, contrast and fog.

[0057]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is hard and has improved desensitization fluctuation and fog over time under high temperature and high humidity.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material comprising a tetrazolium compound having a reactive substituent in the silver halide emulsion layer.