JPS60177339A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide hard contrast and to improve rapidness and stability of a process by incorporating gelatin into a silver halide emulsion layer contained in a hydrophilic colloid layer on a base and incorporating an oxidizing agent having a functional group to react with gelatin into the hydrophilic colloid layer. CONSTITUTION:A hydrophilic colloid layer contg. a silver halide (AgX) emulsion layer is provided on a substrate. Gelatin is incorporated into said AgX emulsion layer and an oxidizing agent having a functional group to react with gelatin is incorporated therein. The functional group to react with the gelatin of such oxidizing agent is exemplified by an active vinyl group, epoxy group, etc. and a tetrazolium compd. is preferably used for the oxidizing agent. The functional group to react with gelatin may be positioned near the oxidizing group of the molecules of the oxidizing agent or may be in the position parted by various bond groups. Good process stability is obtd. and the image having hard and excellent contrast is obtd. by using, for example, a tetrazolium compd. as the oxidizing agent having the functional group reactive with gelatin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a rapid processing developer containing a superadditive developing agent and a relatively high concentration of sulfite. This invention relates to a silver halide photographic photosensitive material (hereinafter abbreviated as photosensitive material) which is improved in terms of image contrast and stability during liquid processing.

(Prior art) The photoengraving process includes a process of converting a continuous tone original into a halftone image, that is, a process of converting a continuous tone density change into a combination of four halftone dots having an area proportional to the density. and a step of converting the halftone dot image obtained in this step into a halftone dot image with better sharpness, a zigzag return step, and the like.

It is essential that the photosensitive side Y1 used in these steps has high contrast in order to obtain good halftone dot quality.

As a method to obtain such characteristics, conventionally, a silver chlorobromide emulsion with relatively fine grains, a narrow particle size distribution, and a high silver chloride content is used to produce a photosensitive material with a very low sulfur salt concentration. A method of processing with an alkaline hydroquinone developer, the so-called lith development method, is known.

However, when this method is used, the storage stability is extremely poor because the concentration of sulfite ions in the developer is low, and rapid processing is not possible because hydroquinone is used as a single active ingredient.

Therefore, processing with a so-called PQ type or MQ type developer containing a relatively high concentration of sulfite, which contains a super-additive type developer that has good storage stability and can be processed quickly, can provide high film stability. It is desired to develop a new optical material that can provide the following.

One of the features related to this new light-sensitive material is that an oxidizing agent made of a tetrazolium compound is contained in a hydrophilic colloid layer including a silver oxide emulsion layer on a support, and this is developed using a superadditive type developer. For example, the processing technology is
-18317, 53-17719 and 53-
No. 17720.

The method of producing silver images with crystalline contrast by processing photosensitive materials containing oxidizing agents such as tetrazolium compounds, which cure all oxidizing properties, with a super-additive type developer is extremely revolutionary compared to conventional technology. It's technology.

However, in the above-mentioned technology, since the photosensitive material contains an oxidizing agent such as a tetrazolium compound that has oxidizing properties, the sensitivity fluctuates during long-term storage or under conditions such as high temperature and high humidity, and the contrast may deteriorate. I like the fact that it has a significant drawback.

Furthermore, when photographing a document through an intersection screen or a contact screen, a particularly high contrast is required, but since the above-mentioned technique does not necessarily provide a sufficiently satisfactory contrast, improvements are desired. was.

(Objective of the Invention) Therefore, the first object of the present invention is to provide a photosensitive material that has high contrast and is excellent in stability and speed of processing. An object of the present invention is to provide a photosensitive material with improved trust deterioration.

(Structure of the Invention) The object of the present invention is to provide a silver halide photographic light-sensitive material in which a hydrophilic colloid layer including a silver halide emulsion layer is coated on a support, at least one of the silver halide emulsion layers.
This can be achieved by using a silver halide photographic material containing gelatin in the hydrophilic colloid layer and an oxidizing agent having at least one functional group in its molecule that reacts with gelatin in at least one of the hydrophilic colloid layers.

The present invention will be explained in more detail below.

The oxidizing agent contained in any one hydrophilic colloid layer according to the present invention is a compound having in its molecule at least one functional group that reacts with gelatin.

Examples of the functional groups of the oxidizing agent that react with gelatin include active vinyl groups, epoxy groups, methanesulfonic acid groups, groups having active halogenes, active esters/l/, J,! :
, an aldehyde group, a maleimide group, an acid halide group, an azolidone, 1. and the like. In addition, in the present invention, the oxidizing agent described in "U" is at a cathode half-wave potential or 10 cm.
Compounds that are more positive than are good and preferred, <Bee) 5 Thulium compounds can be fisted.

In the oxidizing agent according to the present invention having an N fii group in the molecule that reacts with gelatin, the functional group that reacts with gelatin may be located near the group having oxidizing power in the oxidizing agent molecule, and various They may be separated by a bonding group, and furthermore, two or more gelatin functional groups may be present for one group having a solubilizing ability.

The oxidizing agent used in the present invention can be represented by the following general formula [■], and more preferably by the following general formulas [1] to [IV].

General formula [■] [(A)q-(B)Dou(Q)T(R)sGeneral formula [11'
] % formula %: General formula ['1lD General formula [1■] In the general formula CD, A is -Z-(1)=a(2 groups (here, Z is -Co, -+' -NlIC0-, - Each group of C8- or -8O2- Hb t ), -C)T2-
CH-CI-12 group, -08O2CI-IJ.

\(do-COCH2G group, -COOC)(,G group, -8O
2CH, CH2G group.

N represents a hydroxy functional group, but is not limited to these.

B represents a group or atomic group having a valence of two or more, such as a substituted or unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group (e.g. phenylene group, naphthylene group, biphenylene group, etc.)
, represents a divalent or more polyethylene glycol group, a divalent or more heterocyclic group, and a divalent or more atomic group that is a combination of these groups.

Q is a group or atomic group containing an atom pair in which bonds between constituent atoms are broken when oxidizing power is applied, and represents a desensitizing dye π-electron conjugated system or a tetrazolium cation ring.

R is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group (e.g. phenyl group, naphthyl group, biphenyl group, etc.), polyethylene glycol group, hydroxycarbonyl group, carbonyl group, hydroxy group,
It represents an alkoxy group, a mercaptoxy group, a nitro group, an amine/group, a halogen atom, a hydrogen atom, a heterocyclic group, or a monovalent group or atomic group that combines these.

Furthermore, examples of the anion represented by , anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-) toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonate, l-, phosphoric acid anions, and lauryl sulfonic acid anions. Higher alkyl sulfate ester anions such as phate anions, boric acid anions such as tetraphenyl boron, dialkyl sulfosuccinate 7' anions such as di-2-ethylhexyl sulfosuccinate anions, cetylboriethenoxysulfate amines, etc. Examples include polyether alcohol sulfate ester anions, higher fatty acid 7' anions such as stearate anions, and polymers with acid groups such as polyacrylate anions.

L represents an integer of 1 or 2, and represents 1 when the inner salt is cedar bark.

Further, T % m and q are integers of 1 or more, and n and S are integers of 0 or more.

Next, in the general formulas IJD, ' [IID, and [I■], A1, A2, AS and A4 each represent the same group as A in the general formula [1]. Also Q+,
q2, q3 and q4 are integers of 0 or more.
All 4s cannot be 0 at the same time. And B,,B
2, B3 and B4 each correspond to a directly connected group,
The above q+ representing the number of A, , A2, A3 and A4
, Q2, q3 and q4 are 0, the general formula [I
] represents a group having the same meaning as R in ], and q1% q2
, Q3 and q4 represent a number of 1 or more, the general formula [
■] Represents a group having the same meaning as A in []. n, , n2, n
3 and n4 represent an integer of 0 or 1. X is a general formula [
7, L also has the general formula [■]
Indicates a number synonymous with L in . D and E represent a bond or a divalent bonding group.

Next, specific examples of the tetrazolium compounds represented by the above general formulas according to the present invention will be listed (J), but the present invention is not limited only to these.

In the present invention, Upper W (tri-tetrazolium compounds can be used alone or in combination, but when used in combination, the number and types can be combined in any ratio).

In one preferred embodiment of the present invention, the oxidizing agent according to the present invention is a tetrazolium compound, and this compound is added to a gelatin layer containing a silver halide emulsion. In another preferred embodiment of the present invention, it is added to a hydrophilic colloid layer directly adjacent to a silver halide emulsion layer containing gelatin, or to a hydrophilic colloid layer adjacent via an intermediate layer.

In another embodiment, the tetrazolium compound according to the present invention may be mixed with a suitable organic solvent 1, such as alcohols such as methanol and ethanol, or needle hydroxide. It may also be incorporated into a light-sensitive material by dissolving it in an ester or the like and applying it directly to the outermost layer of the gelatin-containing silver halide emulsion layer of the light-sensitive material using an overneat method or the like.

The tetrazolium compound according to the present invention contains I x ]O per mole of silver halide contained in the light-sensitive material of the present invention.
'Mole to 1 mole range, especially JXIO-7 mole to l
It is preferable to use up to Xl0'mol.

Among the above, when added to the silver halide emulsion layer in particular, it can be added at any time after the de-i1:i step of the halide stirrup emulsion manufacturing process, specifically during the physical ripening of the first ripening, or during the second ripening. It is preferable to add it at the end of the second ripening, or before coating the emulsion.

As a method for dispersing the above-mentioned tetrazolium compound in the hydrophilic colloid layer, for example, the method described in U.S. Pat.
．． 676, No. 137, in which the solution is dissolved in a high boiling point organic solvent and then dispersed in the above-mentioned hydrophilic colloid layer;
A method such as dissolving it in dimethyl formaldehyde, ethylene glycol, dioxane, etc. and adding it to the hydrophilic colloid layer coating solution can be applied.

The silver halide used in the photographic material of the present invention may be any silver halide used in ordinary silver halide photographic emulsions, such as silver bromide, silver chlorobromide, silver iodobromide, silver chloroiobromide, and tl chloride. Includes:

Especially when used as a return camera net or a line-sensitive material format,
Preferably, the silver halide composition consists essentially of silver chlorobromide. Even if these silver halides are coarse grained,
Fine particles may be used, and any known method may be used, such as U.S. Pat.
3.317.322, 2.222.264, 3.320.069, 3.206.313 or [Journal of Photographic Science (J, photo, SCi) J No. It can be prepared by the method described in Vol. 12, No. 5 (September and October issues), 1964, pages 242-251. In addition, silver halide prepared by the method 8+'- was mixed with 2
They can also be used together.

Although the silver halide contained in the silver halide emulsion layer of the present invention is not limited, the average grain size is 0.5
~1.0 micron, preferably 01-06 micron, and at least 75%, preferably 80% of the total particle number
It is desirable that the silver halide contains silver halide having a grain size of 0.5 to 1.5 times, preferably 0.6 to 1.4 times, the average grain size.

Further, atoms of gold, iridium, rhodium, osmium, bismuth, cobalt, nickel, palladium, ruthenium, iron, copper, zinc, lead, cadmium, etc. may be contained in these silver halide crystal grains. When these atoms are contained, 10-9 per mole of silver halide
The content is preferably 10-4 moles, particularly 10
It is suitable to contain -8 to 10-4 moles. Further, it may be a surface image type or an internal latent image type. Furthermore, silver halides prepared by different glaze methods may be mixed. The crystal shape may be cubic, octahedral, tetradecahedral, or spherical without any limitations.

The effects of the silver halide grains used in the present invention are the same whether they are negative type or positive type.

The silver halide used in the present invention can be sensitized with a variety of chemical sensitizers. As a sensitizer,
For example, activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea,
selenourea, etc.), reduction sensitizers (triethylenetetramine, F42 tin salt), such as SoJlium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride, ammonium chloroolea Various noble metal sensitized W1.1 represented by date, potassium chlorooleate, sodium chlorovaladite, etc. are each used individually,
Alternatively, two or more types can be used in combination. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

Furthermore, the silver halide emulsion used in the present invention may be optically sensitized using one or more types of sensitizing dyes or desensitizing dyes in order to impart photosensitivity in the desired wavelength range. good. Various sensitizing dyes can be used, but optical sensitizing dyes that can be advantageously used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, and trinuclear or tetranuclear cyanines. kind,
These optical sensitizing dyes include styryls, holopolar cyanines, hemicyanines, oxonols, and hemioxonols, and these optically sensitizing dyes contain bases such as thiazoline and thiazole as part of their structure as nitrogen-containing heterocyclic nuclei. or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, barbituric acid, thiobarbital acid, pyrazolone, etc. Such a nucleus can be substituted with alkyl, hydroxyalkyl, halogen, phenyl\siahalalkoxy, and carbon It may be fused with a radical or a heterocycle. Note that when the above optical sensitizing dyes, particularly merocyanine sensitizing dyes, are used, not only optical sensitization but also the effect of widening the development latitude can be obtained.

The silver halide and gelatin-reactive oxidizing agent according to the present invention are added to the hydrophilic colloid layer, and at least one layer contains gelatin and silver halide. Gelatin is advantageously used as the hydrophilic colloid, but hydrophilic colloids other than gelatin can also be used. Examples of the hydrophilic colloid include colloidal albumin, agar, arabic acid 1, algin N%, hydrolyzed cellulose acetate, acrylamide, imidized polyamide,
Polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, e.g. LJ i country patent 2.6
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in US Pat. No. 14.928, US Pat. No. 2.525.753, etc.
．． Styrene acrylate, acrylic ester, methacrylic acid, methacrylic ester σ-) ethylene group-containing polymerizable monomers as described in No. 520 and No. 2.831.767 were graft-polymerized onto gelatin. These hydrophilic colloids are
It can be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

Supports used in the photosensitive material of the present invention include, for example, baryta paper, polyethylene-coated sheets, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalenite, polyamide films, and polypropylene films. Typical examples include polycarbonate film, polystyrene film, etc., and these supports are selected depending on the intended use of the photosensitive material.

As described above, the light-sensitive material of the present invention has at least one gelatin-containing silver halide emulsion layer on a support, and a parent aqueous colloid layer on the side of the support containing the layer. ``At least one layer contains the ceratin-reactive oxidizing agent related to the present invention, and a protective layer having an appropriate thickness on the layer side, preferably 01 to 10μ, particularly preferably It is desirable that a gelatin protective layer of 08-2/Z is coated.

The hydrophilic colloid layer used in the present invention may optionally contain various photographic additives such as gelatin replasticizer, hardener, surfactant, image stabilizer, Shiyu 1-ray absorber, antistain. additives, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc., within a range that does not impair the effects of the present invention. It can be used in

Among the above-mentioned various additives, those which can be particularly preferably used in the present invention as thickeners or plasticizers include, for example, U.S. Pat. No. 604, Japanese Patent Application Publication No. 1973-
63715, Japanese Patent Publication No. 45-15462, Belky National Patent No. 762.833, U.S. Pat. Hardening agents include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based,
Various hardeners such as vinyl sulfone type, isocyanate thread, sulfonic acid ester type, carbodiimide type, mufuchloric acid type and acyloyl type can be mentioned, and dyes include U.S. Pat.
．． Compounds described in US Pat. No. 990, US Pat. No. 3,048,487, US Pat.

Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent Nos. 548.532 and 1. .216゜389, U.S. Patent No. 3.026.202, U.S. Pat.
No. 43-17926, No. 43-13166, No. 48
-20785, French Painting Patent No. 205.588, Belky National Patent No. 773.459, JP-A-48-101118, etc., anionic, cationic, nonionic or amphoteric compounds can be used. However, among these, anionic surfactants having a sulfone group, such as t-succinic acid ester sulfonates, alkylna-7-talene sulfonates, alkylbenzene sulfones, and the like are particularly preferred. In addition, as an antistatic agent,
-24159, JP 48-89979, JP 2.882.157, JP 2.972.535, JP 48-20785, JP 48-43130, JP 48
-90391, Special Publication No. 46-24159, 46-
No. 39312, No. 48-43809, JP-A-47-3
There are compounds described in British Patent No. 3627, etc., and as matting agents, for example, British Patent No. 1.221.980,
U.S. Patent No. 2.992.101, U.S. Patent No. 2.956.884
No., France Special Freight No. 395.544, Special Publication No. 1973-
Compounds described in No. 43125 etc., especially 05-2
Silica gel with particle size of 0μ, particle size of 0.5-20μ+
Polymers of polymethyl methacrylate and the like can be mentioned.

Examples of the developer that can be included in the developer used in developing the photosensitive material of the present invention include the following.

Typical HO-(C)I=CH)n-OH type developers include catechol, pyrogallol and its derivatives, and ascorbic acid, as well as hydroquinone, chlorohydroquinone, promohydroquinone, isopropylhydroquinone, and toluhydroquinone. methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2+'5-cyhydroxyacetophenone, 2
．． 5-diethylhydroquinone, 2,5-di-p-7enethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3
-Phenylcatechol, 4-phenylcatechol, 3-
-methoxycatechol, 4-acetylpyrogallol, 4
-(2-hydroxybenzoyl)pyrogallol, sodium ascorbic acid, etc.

In addition, typical IO(C)(-CT1)n nI2 type developers include ortho and rose aminophenols or ami/pyrazolones, 4-ami/phenol, 2-ami/-6-phenylphenol, etc. , 2-7 mino-4-chloro-6-phenylphenol, 4-7 mino-2-phenylphenol, 3°4-diami/phenol, 3-methyl-4,6-riaminophenol, 2.
4-diami/resorsonol, 2,4.6-)riaminophenol, N-methyl-p-aminophenol, N-
β-Hydroxyethyl-p-aminophenol, p-hydroxyphenylamine/acetic acid, 2-aminonaphtho-Furthermore, as H2N-(C-C)n-NII type 2 developer,
For example, 4-amino/-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethyl/l/7
= Phosphorus, N-(4-amino-3-methylphenyl)morpholine, p-7 enylenediamine, 4-amino-N,
N-dimethyl-3-hydroxyaniline, N, N,
N', N'tetramethylbaraphenylenediamine, 4
-amino-N-ethyl/'-N-Cβ-hydroxyethyl)aniline, 4-amino/-3-methyl-N-ethyl-N
-(β-hydroxyethyl)aniline, 4-amino-N
-ethyl-(β-methoxyethyl)-3-methylaniline, 4-amino-3-methyl-N-ethyl-N-(β-
methylsulfonamidoethyl)aniline, 4-amino-
N-butyl-N-γ-sulfobutylaniline, 1-(4
-aminophenyl)pyrrolidone, 6-amino/-1-ethyl-1,2,3,4-tetrahydroquinone, 9-aminoyllolidine, etc.; examples of heterocyclic developers include 1-phenyl-3 -pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, 1-(p-amino/phenyl)-3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 5- Examples include ami/uracil, 5-amino-2,4,6-)lyhydroxyphyrimidene, and the like.

Others: The Theory of James, T.H.
The Photographic Process 4th Edition (The 'l
:'theory of the Photography
ic process.

Fourth Edition) pages 291-334 and Journal of the American Chemical
Society 4 (Journal of the AJn
erican Chemical 5ocie-ty)
The developer described in Vol. 73, p. 3100 (1951') can be effectively used in 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. Furthermore, even if a butysulfite salt such as sodium sulfite, potassium sulfite, or ammonium sulfite is used as a preservative in the developer used in the present invention, the effects of the present invention will not be impaired; This can be mentioned as one of the characteristics. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pI-r and providing a buffer function with caustic alkali, alkali carbonate, or amines used in general black and white developers, inorganic development inhibitors such as bromkali, organic development inhibitors such as penttriazole, etc. Metal ion scavengers, development accelerators such as methanol, ethanol, hensyl alcohol, polyalkylene oxide, sodium alkylarylsulfonates, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin. It is optional to add hardening agents such as glyoxal, ionic strength regulators such as sodium sulfate, etc.

The developer used in the present invention may contain alkanolamines or glycols as a solvent for a developing agent or a development inhibitor. Examples of the above-mentioned alkanolamine include monoethanolamine, jetanolamine, and triethanolamine, and triethanolamine is preferably used. The amount of these alkaline amines used is 5 to 500 g, preferably 20 to 200 g, per 11 of the developer solution.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, I,4-butanediol, 1,5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols to be used is 5 to 500 g per 111 of the developer (preferably pumped)
~200g. These organic solvents can be used alone or in combination.

The I) I- (value of the developer having the above composition is 9 to 12, but from the viewpoint of preservation and tensile properties, pf-1 (IH
'4 is preferably in the range of 10 to 11.

The photosensitive material of the present invention can be processed under various conditions. As for the processing temperature, for example, the development temperature is preferably 50°C or lower, particularly preferably around 30°C, and the development time is generally completed within 2 minutes, particularly preferably 1
Within minutes often yields 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 manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

Hereinafter, the present invention will be explained in more detail with reference to Examples. The technical scope of the present invention is not limited to the following embodiment, and many other embodiments are possible.

In particular, in an embodiment of the present invention, a PQ-type super-additive developer is developed, but the present invention is not limited to this.

Example 1 1.0% per mole of mefAJ. OX An aqueous solution containing 10 moles of hexabromorodium potassium salt, sodium chloride, and potassium bromide and an aqueous silver nitrate solution are stirred into an aqueous gelatin solution and mixed simultaneously at \40°C for 25 minutes to form silver chlorobromide emulsion particles. (Contains 98 mol% of silver chloride per mol of silver)
was formed.

This emulsion was added with 2-methyl-4-hydroxy- as a stabilizer.
After adding 570 mg of 1,3,3a,7-titrazaindene compound per mole of silver halide, the mixture was washed with water, desalted, and further sensitized with sulfur.

After sulfur sensitization, a 2-methyl-4-hydroxy-1,3,3a,7-titrazaindene compound was added as a stabilizer to prepare emulsion F as described below.

(Preparation of Emulsion F1 for Preparation) 3 g of a 20% aqueous solution of saponin per 1 mole of silver halide as a coating liquid aid was added to the emulsion prepared as described in Section 2 above, and styrene-maleic acid copolymer was added as a thickener. Add 2I of polymer per mole of silver halide to give 1 silver halide.
The emulsion solution F was prepared by finishing the emulsion to 1.51 per mole.

(Preparation of coating solution) After dividing the emulsion F for preparation prepared as described above into 33 equal parts, exemplified compounds (1) to (6), ((
1) to (29+) and C311 to (36) were added to test samples of surface treatment in an amount of 1X104 mol per mol of silver halide to prepare corresponding coating solutions.

Furthermore, for comparison, a coating solution without any additives and a coating solution to which 2.3.5~triphenyltetrazolium chloride was added in an amount of I X IO-' mol per mol of silver halide, corresponding to the samples in Table 1, were prepared. Each was prepared separately.

Next, the following P1 solution was prepared as a protective armpit solution for emulsion.

(Preparation of PI solution) 1071 kg of gelatin contains 1071 kg of pure water! 4 after swelling.
Heated to 0°C, added 1% aqueous solution of the following compound as a coating aid, and added amorphous silica gel f3 as a matting agent.
0i was dispersed in gelatin and finished in 20.1 to prepare P for a protective film and a coating solution.

(Compound-Z) (Preparation of photosensitive material) On an undercoated polyethylene terephthalate support with a thickness of 100 μm, the emulsion coating solution F+ prepared above, P for peritoneal membrane, and coating solution were combined, and the amount of silver was The test samples shown below (Table 1) were prepared by applying the protective film gelatin so that the amount of gelatin applied was 4p, and the amount of gelatin applied was 1&m2.
It was set as 3. At the time of coating the protective film, two types of hardening agents, formaldehyde and ethyleneimine, were added in combination to the protective film coating solution to form 8 films.

The above test sample was subjected to stepwise exposure according to a conventional method, and then processed in an automatic developing machine having a developing tank capacity of 404 using a developer having the following formulation and a commercially available fixer.

[Development processing conditions]

(Process) ('iJA degrees) (time) Development Heating °C
, 30 seconds fixation 〃 Second water wash Normal humidity Second developer (undiluted solution) Potassium bromide 2.5 g EDTA-2Na 1',! 9 '5Ji potassium sulfate (55% aqueous solution) 90 ml potassium carbonate 25 g hydroquinone 10 g 5-methylbenzotriazole 100 m95-nitrobenzotriazole 100 m9J-phenyl-5-
Mercaptotetrazole 30m? 5-nitroindazole 50m0 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 0.5 g Diethylene glycol 6
0! ! Sodium hydroxide pI-ilo, amount to 6 Add water to finish to 500 m/+ (+)H = 10.6. )
When using, add 500ml of the above stock solution to 5007111 water! Use by diluting with. - Tests on each test sample were conducted immediately after application and in order to observe changes over time. 1. After conditioning the test sample to 5°C and 50% RH, the test sample was sealed in a photographic barrier packaging material and exposed to a 50°C depression (Table 1). -1) In (Table-1), contrast is an indication curve with density 1
It is a value representing the slope between each point obtained from 0 to 25, and represents high contrast. It is clear from the results shown above (Table I) that the test samples according to the present invention (Notifications 3 to 33) to which a tetrazolium compound, which is an oxidizing agent that innogates the gelatin-reactive functional group of the present invention, were not treated. It has good stability and has a significantly higher contrast compared to the comparative sample j≦2 which contains a tetrazolium compound that reacts with gelatin-reactive functional groups, and the deterioration of the image contrast over time has been significantly improved. The results are shown below.

In addition, the number of gelatin-reactive functional groups present in the molecule and the substitution position are such that the color tube is 9 and 41 due to this excellent effect.
Test sample AI, 162, 3, 4
, black 5, jfi 32, J Nibi O 33.

Example 2 An aqueous silver nitrate solution and an aqueous solution containing potassium bromide and sodium chloride were mixed into an aqueous gelatin solution with stirring using a controlled double jet method, and then this emulsion was subjected to gold-hyposensitization and chemically ripened. A silver chlorobromide emulsion (90 mol % of silver chloride per mol of silver) was prepared.

Using the above silver halide emulsion, a preparative emulsion F2 was prepared in the same manner as the above-mentioned Preparation Solution (1).

Next, as a preparation liquid for a protective film for emulsion, a P2 liquid was prepared in the same manner as the P and liquid except that heptalized gelatin was used in place of the gelatin in the P1 liquid. Emulsion F2 and Preparation Solution (2) were coated in the same manner as in Example 1 to prepare test samples Nos. 34 to 38 as shown in Table 2.

Emulsion solution F2 and preparation solution P in the above test sample
The amounts of exemplified compound (1) according to the present invention and comparative 2.3.5-)liphenyltetrazolium chloride to 2 were 1 x 10 per mole of coated silver stone.
The amount corresponds to moles.

The obtained test sample was treated in the same manner as in Example (Table 2).
) From the results shown above, samples j637 and 38 to which the tetrazolium compound according to the present invention was added showed excellent high contrast not only immediately after coating, but also when stored over time, and this high contrast was achieved by adding the tetrazolium compound to the emulsion. It was also found that there was no change even if it was added to the protective film solution.

Example 1 Example 3 An aqueous solution containing 2.0 x 10 moles of hexachlororhodium sodium salt, sodium chloride, and potassium bromide per mole of silver nitrate and an aqueous silver nitrate solution were stirred into an aqueous gelatin solution while performing a controlled double run method. A silver chlorobromide emulsion (containing 80 mol % of silver chloride per mol of silver) with an average grain size of 02 .mu. After washing with water, 12 μl of thiourea dioxide per mole of silver halide was added to this silver halide emulsion at 65° C. in an atmosphere of pH 7.4, and fog-ripened until the highest performance was obtained. .

Using this fogging emulsion, a preparation emulsion Fs was prepared in the same manner as for the F1 preparation. Next, this F,
Test samples 39 to 43 shown below (Table 3) were boiled using the preparation liquid and the preparation liquid P for emulsion retention film in Example-J. Coating was carried out in the same manner as in Example 1.

The above test samples contained exemplified compounds (1), (5) and I29) and 2.3 for comparison in the emulsion coating solution.
゜5-Triphenyltetrazolium chloride coated silver 1
It was added and contained in an amount of I x 10-' mole per mole. The obtained test sample was treated in the same manner as in Example 1, and the results are shown below (Table 3).

(Table 3) As shown in the above table, samples containing the tetrazolium compound according to the present invention exhibit excellent contrast properties both in direct positive photosensitive materials, immediately after application, and when stored over time. Understood.

(Effects of the Invention) The photosensitive material of the present invention, in which the hydrophilic colloid layer contains the oxidizing agent of the present invention having a functional group reactive with gelatin in its molecule, has good processing stability; It is also stable and exhibits excellent hardness even during long-term storage.

Agent Patent Attorney No 1) Salary Arata

Claims (2)

[Claims] (1) In a silver halide photographic material in which a hydrophilic colloid layer including a silver halide emulsion layer is coated on a support, at least one of the silver halide emulsion layers contains gelatin, and the hydrophilic colloid layer contains gelatin. A silver halide silver halide (I) [F] optical material format, characterized in that at least one of the sexual colloid layers contains an oxidizing agent having at least one functional group in its molecule that reacts with gelatin. (2) The silver halide photoreceptor according to claim 1, wherein the oxidizing agent is a tetrazolium compound.