JPH0237340A - Silver halide photographic sensitive material capable of obtaining high contrast and high dot quality picture - Google Patents

Abstract

PURPOSE:To obtain the title material which has a less tendency for generating a fog and high sensitivity and is capable of obtaining a picture with high contrast and high dot quality by incorporating an oxyborane compd. in the photosensitive material contg. a hydrazine compd. CONSTITUTION:The oxyborane compd. and the hydrazine compd. are incorporated jointly in the photosensitive material. The oxyborane compd. means a compd. which binds alkylene oxide or arylene oxide to a boron atom, and is incorporated in an optional layer such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, an under coating layer, an auxiliary layer, an irradiation preventing layer and a rear coating layer, etc., in addition to a silver halide emulsion layer, and most preferably the outermost layer of the photosensitive material. The effect of incorporating the oxyborane compd. in the layers is lessened according to a layer closer to a supporting body in succession. However, the effect can be controlled by the compounding amount and the kind of the oxyborane compd. Thus, the picture which ha the less tendency for generating the fog and the high sensitivity and contrast, is obtd., and the photosensitive material having the high dot quality is obtd. in spite of the dimension of a dot area.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and in particular, it has low fog, high sensitivity, high contrast photographic images, and high quality halftone dots. This invention relates to a silver halide photosensitive material that can be stably obtained.

[Conventional technology]

In the field of silver halide photographic light-sensitive materials, light-sensitive materials that produce high-contrast images are sometimes used depending on the application. , high-contrast photographic images are used to form fine line images. The types of silver halide photographic materials for this purpose include:
It is known that extremely high contrast photographic images can be formed.

Conventionally, for example, a photosensitive material consisting of a silver chlorobromide emulsion with an average grain size of 0.2 μm, a narrow grain distribution, a uniform grain shape, and a high silver chloride content (at least 50 mol %) has been processed using sulfite ions. Images with high contrast, high sharpness, and high resolution, such as halftone dot images or fine line images, are obtained by processing with an alkaline hydroquinone developer having a low concentration.

This type of silver halide photosensitive material is known as a lithium-type photosensitive material.

The photolithography process involves converting a continuous-tone original into a halftone image, that is, converting the continuous-tone density changes of the original into a set of halftone dots with an area proportional to the density. There is.

For this purpose, a dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing the original through an intersection line screen or a contact screen, followed by development processing.

For this purpose, a silver halide photographic material containing a silver halide emulsion with fine grains and a uniform grain size and shape is used. When processed with a black and white developer, the quality of halftone dots etc. is inferior to when developed with a Lith type developer. Therefore, the sulfite ion concentration is extremely low, and it is processed with a developing solution called a Lith type developer that uses hydroquinone as a developing agent. However, since the lithium-type developer is susceptible to auto-oxidation and has extremely poor storage stability, a control method is required to maintain constant development quality even during continuous use. Much effort has been made to improve constancy.

To maintain the stability of the above-mentioned Lith-type developer, we have developed a replenisher (processing fatigue replenisher) that compensates for the deterioration in activity due to development processing, and a replenisher (processing fatigue replenisher) that compensates for the oxidative deterioration over time to maintain the stability of the above-mentioned Lith-type developer. The so-called two-liquid separation replenishment method, in which the replenisher (fatigue replenisher) and the replenisher (fatigue replenisher) are replenished using separate replenishers, is generally widely adopted in automatic developing machines for photolithography and the like. However, the above method has the problem that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

On the other hand, a method is known in which a high contrast image is obtained by processing with a developer having a high sulfite ion concentration.

The above method involves incorporating a hydrazine compound into a silver halide photographic light-sensitive material.

According to this method, it is possible to maintain a high concentration of sulfite ions in the developer, and it is possible to stably process with improved preservation.

However, the developer used for silver halide photographic light-sensitive materials containing hydrazine compounds requires a relatively high pH value in order to obtain high contrast, which tends to cause fog. There is a problem in that sensitivity is sacrificed as a result of containing various organic inhibitors in high concentrations.Therefore, there is a strong demand for silver halide photographic materials that can provide high contrast images and have low fog and high sensitivity. It is rare.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material containing a hydrazine compound that has low fog, high sensitivity, and high contrast images, and that provides high quality halftone dots regardless of the size of the halftone dot area. An object of the present invention is to provide a silver halide photographic light-sensitive material from which dots can be obtained.

[Structure of the invention]

The object of the present invention is achieved by a silver halide photographic material containing a combination of an oxyborane compound and a hydrazine compound.

In this way, the present invention provides a photosensitive material that has low fog and high sensitivity, and can provide images with high contrast and high halftone dot quality by incorporating an oxyborane compound into a silver halide photographic light-sensitive material containing a hydrazine compound. was developed.

According to the present invention, as an additional effect, the antistatic properties of the photosensitive material can be improved.

The present invention will be explained in more detail below.

First, the oxyborane compound contained in the photosensitive material of the present invention will be explained. Here, the oxyborane compound is
A compound in which alkylene oxide or arylene oxide is bonded to a boron atom. Preferred oxyborane compounds include those represented by the following general formula [1].

R1+ Here, RIl+R1□ and RI3 each represent an optionally substituted alkyl group, aromatic group, or heterocyclic group.

Preferred specific examples of oxyborane compounds that can be used in carrying out the present invention will be listed below, but the invention is not limited thereto.

11 to l! (1-CG+tHz≦ In the photosensitive material of the present invention, the oxyborane compound can be contained at any location. In other words, the photosensitive material generally includes a support and at least one halogenated layer provided on at least one surface of the support. It is composed of a silver emulsion layer, and other layers other than the silver halide emulsion layer include a protective layer, an intermediate layer, a filter layer, an anhalation layer, an undercoat layer, an auxiliary layer,
It may have an irradiation prevention layer, a backing layer, etc. as appropriate, and the oxyborane compound can be contained in any of these layers. Among these, it is most preferable to use it in the outermost layer, and the effect decreases as the layers get closer to the support, but it is possible to adjust the amount and type of addition to 1N.

For example, it is a preferred embodiment that it is contained in the protective layer,
In this case, the oxyborane compound is 0.1 g to 10 g'/
It can be preferably used within the range of %. It is also preferable that the compound be contained in the silver halide emulsion layer, and in this case, it is appropriate to add this compound preferably in an amount of 10-h to 10 mol per 811 mol in the silver halide emulsion. preferably 10-'-10-'' mole addition),
When adding these, they can be dissolved in alcohols such as methanol and ethanol, ethers, ketones, glycols such as enalene glycol and diethylene glycol, and then added to the emulsion. Also, it can be added to the layer adjacent to the emulsion layer without being added directly to the emulsion.
It may be contained by being diffused into the emulsion layer side.

Examples of the hydrazine compound preferably used in the present invention include compounds represented by the following general formula (U) or general formula (111).

General formula [■] General formula (Ill) RINII
NHCIIOR+NHNHCORzIn the formula, l(+ and R
1 is the number of a pyridyl crystal, a quinolyl group, a furan group, a naphthane ring, etc., and these groups include an aryl group, an alkyl group, a substituted ureido group, an aliphatic amino group, a halogen atom, an alkoxy group, an alkylamino group, etc. may be substituted with a group of Further, R and R1 represent an optionally substituted aryl group (eg, phenyl group, naphthyl group, etc.) or an optionally substituted alkyl group.

The aryl group represented by R9 and R2 contains a benzene ring or a naphthalene ring, and this ring may be substituted with various substituents. Preferred substituents include a straight chain or branched alkyl group (preferably a carbon (numbers 1 to 20, such as methyl group, enal group, isopropyl group, n-dodecyl group, etc.)
, alkoxy groups (preferably those having 1 to 20 carbon atoms, such as methoxy crystals and ethoxy groups), aliphatic acylamino groups (preferably those having alkyl groups having 2 to 21 carbon atoms, such as acenalamino group, hebnalamino group, etc.) , aromatic acylamino groups, etc. In addition to these, for example, substituted or unsubstituted aromatic rings such as those mentioned above may be used as -CONt
l, S, 0, 5 (hNH, NH
CONH(:HzCHN-) also includes those bonded with a linking group.

Hydrazine compounds are disclosed in U.S. Pat. No. 4,269,92
It can be synthesized with reference to the description in No. 9.

The hydrazine compound can be contained in the emulsion layer or in the hydrophilic colloid layer adjacent to the emulsion layer, or even in other hydrophilic colloid layers, but is preferably contained in the emulsion layer or in the layer adjacent to the emulsion layer. It is to make it contain.

The hydrazine compound can be added after being dissolved in alcohols such as methanol and ethanol, glycols such as enalene glycol and diethylene glycol, ethers, ketones, etc., and the amount of addition is 1 mole of silver halide. The range is preferably from 10-h to 10-1 mol, more preferably from 10-4 to 10-2 mol.

Examples of particularly preferred hydrazine compounds are as follows. It goes without saying that the present invention is not limited to the following compounds.

■-Formy-2-phenylhydrazine CH-2> ■-Formy-2- (4-methoxyphenyl)hydrazine (H-3) 1-Formyl-2-(4-bromophenyl)hydrazine (H-4) 1-Formyl- 2-(4-enalphenyl)hydrazine (H-5) 1-formyl-2-(4-methoxyphenyl)hydrazine (l(-6) l-formyl-2-(4-acetamidophenyl)hydrazine (H-7 ) ■-Formy-2-(4-butylamidophenylhydrazine (H-8) 1-formyl-2-(4-(2-(2,4-diter)
t-pennalphenoxy) bunalamide] phenyl) hydrazine (l(-9) ■-formyl-2- (4-dimethylaminophenyl)
hydrazine ()i-10) ■-formyl-2- (4-acetamido-2-menaluphenyl)hydrazine 1-formyl-2-(4-(3-phenyl-thioureido)phenyl)hydrazine (I(-12) 1 -Formyl-2-(4-(3-enalothioureido)phenyl]hydrazine (H-13) 1-Formyl-2-(4-(4-(3-phenylthioureido)phenyl)carbamylphenyl)hydrazine (l(-14) ■-formyl-2- (4-(3-(4,5-dimenalnaazol-2-yl)thioureylene)phenyl)hydrazine (H-15) 1-formyl-2-(4- (Phenylthiocarbamyl)
phenyl]hydrazine1-formyl-2-(4-(N-methylbenzothiazol-2-yl)naourylenephenyl]hydrazine (H-17) 1-formyl-2-((4-(1,3- Dumenalbenzimidazole-2-yludiureylene phenyl)
hydrazine 1-formyl-2-((4-(5-methyl-2-thio-
imidacillin-3-yl)phenyl])hydrazine (H-19) 1-formyl-2-((4-(3-n-butylureido)phenyl)hydrazine 1-formyl-2-(4-(3-(p -chlorophenyl)ureido]phenyl)hydrazine ()l-21) 1-formyl-2-(4-(3-(p-(2mercapto-tetrazol-3-yl)phenylkothioureylene)phenyl)hydrazine (H -22) ■-Formyru2 (4-(ω-(N-sulfopropylbenzothiazol-2-yl)propylaminocophenyl)hydrazine ()l-23) 1-(p-chlorobenzoyl)-2-phenylhydrazine ()l-24) 1-(p-cyanobenzoyl)-2-phenylhydrazine 1-(p-carboxybenzoyl)-2-phenylhydrazine 1-(3,5-dichlorobenzoyl)-2-phenylhydrazine (H- 27) l-(2-formylhydrazino)-4-(N-dimethylami/)Hensen (H-28) 1-(2-formylhydrazino)-4-(2formylhydrazino)benzylbenzene (H-29 ) Various silver halides can be used in the silver halide emulsion layer used in the silver halide photographic light-sensitive material (hereinafter also simply referred to as light-sensitive material) of the present invention.For example, silver chloride,
These include silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. The effect of the present invention is particularly remarkable for silver bromide and silver iodobromide, and is particularly effective for high-sensitivity light-sensitive materials containing a small amount of silver iodide (eg, 5 mol % or less of Agl).

The silver halide emulsion of the silver halide emulsion layer of the light-sensitive material of the present invention may be prepared by using a silver halide emulsion suspended in a hydrophilic colloid by various methods, such as a single emulsion by a neutral method or an ammonia method. Emulsion preparation methods such as jet method and double jet method are used.

The silver halide contained in the silver halide emulsion layer used in the light-sensitive material of the present invention has an average grain size of 0.01 to 1.0.
μm is preferable, particularly preferably 0.05 to 0.7 μm.
m, and preferably at least 75%, particularly preferably 80% or more of the total number of grains contain silver halide having a grain size of 0.7 to 1.3 times the average grain size. Note that the particle size is expressed in terms of the diameter of a circular image having an area equal to the projected area of the particle.

Furthermore, as silver halide emulsions in which polyvalent metal ions such as iridium and rhodium are occluded, U.S. Pat.
．． Emulsions such as those disclosed in No. 531,291 can also be used. Silver halide emulsions are made from sulfur compounds, gold compounds (
Sensitization can be carried out by chemical sensitization using chloroauric acid salts, gold trichloride, etc.).

In the silver halide emulsion layer or other hydrophilic colloid layer, alkyl acrylate, alkyl methacrylate,
A polymer latex consisting of a homopolymer or a copolymer of acrylic acid, glycidyl acrylate, etc. may be included in order to improve the dimensional stability of the photographic material and the physical properties of the film.

The silver halide emulsion to which the present invention is applied can be imparted with color sensitivity in a desired wavelength range using a sensitizing dye. As the sensitizing dye, commonly used ones such as menane dyes and sunaryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxanol, and hemioxonol can be used.

In the silver halide emulsion applied to the present invention, the following general formula (IV) or (V
) are useful.

General formula [1■] General formula (V) In the formula,
R□R,, RC and R6 may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyan group, a hydroxyl group, a carboxyl group, an alkoxy group, an acyl group, or a substituted or unsubstituted Represents a substituted alkyl group, aryl group or heterocyclic group, and Hb and Rc
may be combined to form a 5- or 6-membered closed ring structure.

Specific examples of compounds represented by the above general formula include the following. It goes without saying that the present invention is not limited to these specific compounds.

(S-1) 4-Hydroxy-6-menaloo 1.3.3a, ? −
Tetrazaindene (S-2) 4-hydroxy-5-ethyl-6-menal L: L3a+
7-tetrazaindene (S-3) 2-mercaptomenal-4-hydroxy-6menalu 1
．． 3.3a, 7-tetrazaindene (S-4) 2-carboxy-4-hydroxy-6-menal 1+J+
Ja+ 7-tetrazaindene (S-5) 2.4-dihydroxy-6-menaloo 1.3.3a.

7-tetrazaindene (S-6) 2-amino-5-carboxy-4-hydroxy 1.3.
3a, 7-tetrazaindene (S-7) 5-carboxy-4-hydroxy-1+ 3* J a
l 7-tetrazaindene (S-8) 2-nonal-4-hydroxy-6-menalu 1°a+3
a+7-tetrazaindene (S-9) 4-hydroxy-5-cyano-1,3,:(a, 7-
Tetrazaindene (S-10) 3-chloro-4-hydroxy-6-methyl-1°3.3
a.? -tetrazaindene (S-11) 2,4-dihydroxy-6-menaloo 1.3.3a,
7-tetrazaindene (S-12) 1,2-bis(4-hydroxy-6-menalu 1, (
, Ja, 7-tetrazainden-2-yl)l 2-dihydroxyethane (S-137 5-amino-7-hydroxy-2-p-methoxyphenyl-1,2,3,4,6-pentaazaindene The above compounds can be added during and/or at the end of physical ripening of silver halide in the emulsion formation process.These compounds are added during the process of growing and forming silver halide in a hydrophilic colloid layer such as gelatin. Furthermore, it may be added immediately before, during and/or after chemical ripening, or it may be added at the time of preparing the coating solution.The preferred method of addition is boat fishing, in which halogen It is added in a range of 10-'' to 10-' mol per mol of silveride, more preferably in a range of lo-4 to 10-2 mol.The above compound is added to the emulsion. In this case, it can be added by dissolving it using a similar solvent in accordance with the method used when adding the compound represented by the general formula [1] or the hydrazine compound.

Further, in the photosensitive material of the present invention, an antifoggant or a stabilizer having the following general formula [■1] or [■] general formula [V!
] General formula [■] Ar -OHHO-Ar-
(IH [In the formula, Ar represents an aromatic ring, and the aromatic ring is an alkyl group (having 1 to 15 carbon atoms), a halogen atom, a hydroxy group, a hydroxyalkyl group (the alkyl group is substituted with a hydroxy group or a halogen atom) may be substituted with an aldoxime group, etc.), a remarkable fog-inhibiting effect can be obtained when a compound having the structure shown in the following is used in combination.

Specifically, the following compounds can be mentioned. It goes without saying that the present invention is not limited to these specific compounds.

(1) Hydroquinone (2) Methylhydroquinone (3) Chlorohydroquinone (4) Hydroquinone monosulfonate (5)
2.5-Dienalhydroquinone (6) 1.4-
Dihydroxynaphthalene (7) 2,3-Dihydroxynaphthalene (8) Gennasaldoxime (9) 2,5-Dihydroxyacetophenone ochim (10) Gennasamide (11) N-Menalgenasamide (12)
N-(β-hydroxyenal) gennasamide (13) N-(n-hexadecyl) gennasamide (14) salicylaldoxime (15) resorcyaldoxime (16) hydroquinone monohenzoate (17) hydroquinone aldoxime The above compounds are , U.S. Patent No. 2,675
．． No. 314, British Patent No. 623.448, Japanese Unexamined Patent Publication No. 1983
It can be synthesized by referring to the description in No.-11029 and the like.

In order to add these additives to the silver halide emulsion, known methods for preparing additives can be used. That is, it may be dissolved in alcohols such as methyl alcohol and enal alcohol, ethers (dienal ether, dipropyl ether), ketoso compounds such as acetone, dioxane, petroleum ether, or nonionic, anionic, and canonical surfactants. It may be added after being dispersed in a high boiling point solvent.

The silver halide manuscript emulsion applicable to the present invention includes aldehydes (formaldehydes, glyoxals, glutaraldehydes, mucochloric acid, etc.), N-menarol compounds, etc., which are commonly used as hardening agents! # (dimethylol urea, methyloldimenalhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.),
Active vinyl compound (1,3,5-)lyacroyl-hexahydro-S = nitriazine bis(vinylsulfonyl)
Methyl ether, etc.), active halides (2,4-dichloro-6-hydroxy-3-triazine, etc.), etc. can be used alone or in combination, and are commonly used as thickeners, matting agents, coating aids, etc. You can use whatever is used. Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

Supports used include baryta paper and polyenalene.
Covering paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc. can be selected as appropriate depending on the intended use of the photosensitive material.

The photosensitive material of the present invention uses 80- (CH=C
Commonly used developers such as H), -OH type, HtN(L=L)n NHz type, and heterocycle-containing developers can be used.

Typical examples of the i+o-(Cn=C)l), -011 type developer include catechol, pyrogallol and its derivatives, and ascorbic acid, as well as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone,
Examples include methylhydroquinone.

Typical flu (ell = CH), INHz type developers are ortho and para aminophenols or aminopyrazolones, 4-aminephenol, 2-amino-6-phenylphenol, 2-amino-4-chloro -6-phenylphenol, 4-amino-
2-phenylphenol, 3.4-diaminophenol, 3-nonal-4.6-diamitphenol, 2.4-
Examples include cyamyl sorcinol, 2,4,6-triaminophenol, N-nonal-p-aminephenol, and the like.

As a developer having a heterocycle, for example, 1-phenyl-
3-Pyrazolidone (Phenidone), ■-Funiru 4-
Amino-5-pyrazolone, 1-(p-aminophenyl)-
3-amino-birapurin, 1-phenyl-2-nonal-4-amino-5-pyrazolone, 1-phenyl-4,4'
-dimethyl-3-virazolidone (dimezone), 1-phenyl-4menal-4-hydroxynonal-3-pyrazolidone (dimezone-S), and the like.

Others, 'l', L James, The Theory
Of the Photographic Process 4th Edition ('l'
he 'l'heory of the Photog
rapic Process+1'outh Ed
ition), pp. 291-334 and Journal of the American Chemical Society (Journ
al of the American Chemistry
al 5ociety) Volume 73, Page 3110 (19
51) 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. A preferred combination is a combination of hydroquinone and phenidone or hydroquinone and dimezone, where hydroquinone is 5 g to 80 g/It, phenidone or dimezone is 0.05 g/It, and the developer used in the photosensitive material of the present invention contains a preservative such as sulfite. Even if sulfites such as soda, potassium sulfite, and ammonium sulfite are used, the effects of the present invention are not impaired and can be cited as one of the features of the present invention. Suitable sulfite concentration is 0.06 to 1 gram ion/Il. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives.

In addition, pH adjustment and buffering functions are provided using caustic alkali, alkali carbonate, or amines used in general black and white developers, inorganic development inhibitors such as brompotali, metal ion scavengers such as enalediaminetetraacetic acid, methanol, Development accelerators such as ethanol, benzyl alcohol and polyalkylene oxide, surfactants such as sodium alkylarylsulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardeners such as glitaraldehyde, formalin and gluoxal. It is optional to add ionic strength adjusting agents such as , sodium sulfate, etc. The pH value is preferably generally between 9 and 1
2 can be set arbitrarily, but from the viewpoint of stability and photographic performance, pi
-ii.

It is more preferable to use the range of 11 to 11.

The photosensitive material of the present invention can be processed with a developer under various conditions, but the development temperature is preferably 50°C or lower;
In particular, the temperature is preferably around 40°C, and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which often brings about good results. Processing steps other than development,
For example, it is optional to adopt steps such as washing with water, stopping, stabilizing, fixing, and further, if necessary, pre-hardening and neutralizing, 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.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

However, the technical scope of the present invention is not limited in any way by the following examples, and various embodiments are possible.

In particular, embodiments of the present invention will be explained using a high-sensitivity silver halide photographic light-sensitive material, a so-called darkroom type silver halide photographic light-sensitive material, but the present invention is not limited thereto in any way.

Example 1 A silver iodobromide emulsion (1 mol % of silver iodide per 1 mol of silver) was prepared by the simultaneous mixing method.The average grain size was 0.28 μm, and this emulsion was washed with water and desalted in a conventional manner, and then sulfur aggravated. and 4-hydroxy-6-menalium as a stabilizer after sensitization 1.3.
1.5 g of 3a,7-chitrazaindene, 3 g of hydroquinone and 2 g of resorcinaldoxime were each weighed per mole of silver.

Furthermore, 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole were added as fog suppressants to silver 1.
o per mole, 1 g, Anthitro 5 as aggravating pigment
．． 200 g/(silver 1 mol) of 5-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was added, and saponin was added as a coating aid to Ig/(silver). 1 mol), 200 ng of Sunalene-maleic acid copolymer as a thickener.
/ (1 mole of silver) was added to prepare an emulsion. 12 times this emulsion
Divide into oxyborane compounds shown in Table 1 or comparative compounds thereof (a, b, c below) and Table 1
A hydrazine compound was added to prepare an emulsion coating solution.

The oxyborane compound is 3XlO-'mol/(1 mole of silver)
, compounds a, b, and c were each added in an amount of 3 Xl0-3 mol/(1 mol of silver).

, i Yu, Pa J Next, a coating solution for an emulsion protective film was prepared as follows. That is, 10 β of pure water was added to IKg of gelanan, heated to 40°C after swelling, and 30 g of a polymer of menal methacrylate (average particle size 0.27 μm) was dispersed in gelatin as a matte. The coating solution for the protective film was prepared by finishing the coating solution.

The emulsion coating solution prepared above and the coating solution for the protective film were combined on a polyenalene terephthalate support with a thickness of 100 μm that had been subbed with halogen, and the silver amount was 3.5 g/rd by simultaneous multilayer coating. The amount of gelanan attached is 1.8g/m
Also, the amount of gelanan added to the protective layer was 1.1g/
m, and sample floors 1 to ff1 shown in Table-1.
12 was created. During multilayer coating, three types of hardening agents were added to the protective film coating solution: formaldehyde 205g/(per gram of gelanan), mucochloric acid 20mg/(per gram of gelanan), and enalenimine It)s+g/(per gram of gelanan). It was hardened.

These samples were subjected to stepwise exposure to xenon light through a commercially available normal contact screen (gray negative 150 line), and then developed using the developer formulation shown below. The fixer used was a commercially available rapid fixer. The development processing conditions are: development at 40°C for 20 seconds, and fixing at 35°C for 20 seconds.
The washing time was 20 seconds at room temperature.

(Developer formulation) (Comparative compound) +a+ Polyethylene glycol (enalene oxide chain n-10) (bl Polypropylene glycol (propylene oxide chain n = 8) (C1 nonyl phenoxyborienalene glycol (polyethylene glycol chain n = 12) ) 'ILIL Uni-wide Halftone area of the above treated samples 10%, 50% and 9
The quality of each halftone dot of 5% was evaluated in five grades by visual observation using a 100x magnification looper. As for the evaluation score, "1" is the lowest quality, the quality is higher in order, and the rank "5" indicates the best level.

Science and engineering The measurement results are shown in Table -■.

As is clear from Table 1, sample fish 4 to 12 of the present invention can obtain high-quality halftone dots by using an oxyborane compound, especially a compound represented by the general formula (IJ), and a hydrazine compound in combination. It was found that high sensitivity and good capri characteristics were obtained.

On the other hand, samples 1 to 3 for comparison cannot obtain high-quality halftone dots, have poor sensitivity, and have poor fog characteristics.
Example-2 In order to confirm the effect of the stabilizer, all examples were carried out except that hydroquinone and resorcinaldoxime were not used.
A sample light 13 was created in the same manner as the sample light 9 of No. 1. In addition, Sample 14.15 was prepared in the manner shown in Table 3 with 1 per mole of hydroquinone or hydroquinodi and resorcinaldoxime used in emulsion preparation.

The measurement results are shown in Table-2. Table 2 shows that sample m14.15 to which hydroquinone or hydroquinone and resorcinaldoxime was added had better fog suppression than sample m13 to which these compounds were not added [Effect of the invention] As stated above, the present invention For example, in a light-sensitive material containing a hydrazine compound, sensitivity and contrast are improved, and high-quality halftone dots can be obtained regardless of the size of the halftone dot area.

Claims (1)

[Claims] 1. A silver halide photographic material containing a combination of an oxyborane compound and a hydrazine compound.