JPH0444026A - Silver halide photographic sensitive material improved in pressure resistance and processing method - Google Patents

Abstract

PURPOSE:To obtain an ultra-rapid processing property and to improve pressure resistance by specifying the residual amt. of an org. settling agent after desalting to 0.1 to 8.0g per 1mol silver halide and specifying the weight ratio of the silver and gelatin in hydrophilic colloidal layers to >=1.0. CONSTITUTION:The residual amt. of the org. settling agent after desalting is specified to 0.1 to 8.0g per 1mol silver halide and the weight ratio (Ag/gelatin) of the silver and gelatin in the hydrophilic colloidal layers on the side contg. silver halide emulsion layers of the silver halide photographic sensitive material with respect to a base is specified to >=1.0. The gelatin amt. refers to the total sum of the gelatin amts. of >=1 layers on the side contg. the photosensitive silver halide emulsion layers and the silver amt. is defined for the total silver amt. of the respective layers. The excellent pressure resistance is obtd. even in the ultra-rapid processing in this way and the silver in the photosensitive material is effectively utilized. In addition, hard-contrast images are obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic light-sensitive material having ultra-rapid processing suitability and improved pressure resistance, and processing. Regarding the method.

[Background of the invention]

In recent years, in order to cope with the increase in the amount and speed of information as part of the information industry, demands for rapid processing of silver halide photographic materials have become extremely strict even in the printing industry. ■In order to improve work ease and stability,
The so-called lithographic development, which has been commonly used in the development of conventionally printed photosensitive materials, has been replaced by rapid access development, which improves its shortcomings in stability. By incorporating the agent into the silver halide emulsion, it is possible to achieve high contrast equivalent to lithographic development, and
Development time of 0 to 30 seconds became possible. However, the above requirements further include a strong requirement for development in 20 seconds or less2, and of course, a reduction in image quality is unacceptable. On the other hand, in printing, there is an operation called power reduction, so it is not possible to reduce the amount of silver simply for the purpose of speeding up the process.

Therefore, for rapid processing and silver saving, it is important to develop silver halide in a short time without waste and to utilize it effectively. Considering rapid processing and silver saving, it is necessary to reduce the amount of gelatin, but reducing the amount of gelatin generally causes deterioration in pressure resistance. Therefore, there is an extremely strong demand for silver halide photographic materials and processing methods that are capable of ultra-quick development, save silver, and have improved pressure resistance.

[Purpose of the invention]

In view of the above-mentioned problems, the object of the present invention is to provide a silver halide photographic material that has excellent pressure resistance even in ultra-rapid processing, allows the silver in the material to be effectively developed, and provides high-contrast images. The object of the present invention is to provide a processing method.

[Structure of the Invention] The object of the present invention is to desalt the organic precipitant in a silver halide photographic light-sensitive material containing a silver halide emulsion obtained by coagulation and desalting with an organic precipitant. The amount remaining after the treatment is 0.1 to 8.0 g per mole of silver halide, and in the hydrophilic colloid layer on the side of the support containing the silver halide emulsion layer of the silver halide photographic light-sensitive material. This was achieved by a silver halide photographic material characterized in that the weight ratio of silver to gelatin (Ag/gelatin) is 1.0 or more.

Furthermore, the negative-working silver halide photographic light-sensitive material of the present invention is processed within a developing time of 19 seconds, and is dry.

It is characterized in that the total dry processing time is 20 seconds to 60 seconds.

Detailed Description of the Present Invention In the present invention, Dry to Dry refers to the total time from when the leading edge of a photosensitive material is inserted into an automatic developing machine, through development, fixing, washing with water, and drying until the leading edge emerges from the automatic developing machine. It is. In other words, the quotient (see) obtained by dividing the total length of the processing line (m) including various crossing parts by the line conveyance speed (m/sec)
, and is characterized in that the value is 60 seconds or less.

In addition, in the embodiment of the present invention, the amount of gelatin refers to the amount of gelatin on the side containing the photosensitive silver halide emulsion layer with respect to the support.
This refers to the total amount of gelatin in the layers and is not limited to the amount of gelatin in the silver halide emulsion layer. In addition, when a plurality of layers are coated on the same side of the support, the amount of silver is defined based on the total amount of silver in each layer.

The light-sensitive material of the present invention contains a silver halide emulsion obtained by coagulation and desalting with an organic precipitant, and the residual amount of the organic precipitant after desalting is 0.1 to 1 mole of silver halide. 8.
0g.

If the residual amount is less than 0.1 g, sedimentation properties will deteriorate. Moreover, if it exceeds 8.0 g, the effect of the present invention cannot be changed. This residual amount is preferably from 0.1 to 5.0 g per mole of silver, more preferably from 0.1 to 3 g.
．． It is 0g.

In the present invention, any organic precipitant can be used.

The organic precipitants that can be used are illustrated below, but are not limited thereto.

First, the use of organic polymers or non-polymeric sulfonic acids or sulfuric acids that function as coagulants, such as naphthalene disulfonic acid, polystyrene sulfonic acid and derivatives, long chain alkyl sulfonic acids and sulfuric acids, such as various anionic wetting agents. I can do it.

Secondly, a sulf7onated product of phenolic aldehyde resin can be used. This is excellent because it is not significantly affected by the pH of the emulsion, causes flocculation and precipitation with a small amount of addition, and does not have an adverse effect on emulsion performance. Furthermore, since it has the effect of increasing the viscosity of the gelatin emulsion, the amount of gelatin in the emulsion can be reduced, making it possible to produce a high-performance light-sensitive material. This viscosity increasing effect is less affected by pH and is stable. Examples of such compounds include resins obtained by combining phenols such as phenol, cresol, resorcinol, and naphthol with aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde, and then adding 5 to 10 times the amount of concentrated sulfuric acid or Examples include those obtained by heating with fuming sulfuric acid to a temperature of around 100°C to form a sulfonate. Note that these sulfonated resins can also be obtained by first converting the raw material phenol into a sulfonated product and then condensing it with an aldehyde. Regarding the degree of condensation of this resin, those with a low condensation degree have a narrow pH range in which the emulsion can coagulate and precipitate and are difficult to handle, while those with a high degree of condensation tend to be easily colored during resin production and have an excessive thickening effect. Generally, those having an average degree of condensation of 2.5 to 8 are preferred. The degree of sulfonation may be as high as necessary to form an aqueous solution of these resins, and resins containing 20 to 60% by weight of bound sulfuric acid are preferred.

Third, as an organic precipitant, a copolymer of a compound selected from sodium, potassium, and ammonium salts of paravinylbenzenesulfonic acid and a compound selected from vinyl compounds represented by the following general formula (A). can be used.

General formula (A) CH2=CH Here Z is or -CONHR' (R'1iCH20t(.

-CH20CH3, -CH2=CH, or fourthly, a polymer of 2 acrylamide 2-methylpropanesulfonic acid or its salt (I) or (
A copolymer of I) and a vinyl compound represented by the following general formula (II) can be used.

General formula (I) CH8 CH2-CHCoNHC-CH2=CHCH3 where M is hydrogen, Li, Na, K, NH, R1+
R2+R3 is represented, and Rl, R2, and R3 each represent alkyl or substituted alkyl having 5 or less carbon atoms. However, the total number of carbon atoms in R1°R- and R8 must exceed 10 (mana 1/).

Representative examples of 2-acrylamido-2-methylbronosulfonic acid or its salts include: 2-acrylamido-2-methylpronosulfonic acid 2-acrylamido-2-methylpronosulfonic acid potassium 2-acrylamido-2-methylpronosulfonic acid 2-acrylamido-2-methylpronosulfonic acid Examples include sodium 2-acrylamido-2-methylbronosulfonic acid ammonium 2-acrylamido-2-methylbrono(sulfonate triethylammonium 2-acrylamido-2-methylbronosulfonate bishydroxymethylammonium sulfonate, but are not limited to these) isn't it.

Typical examples of vinyl derivatives that may be polymerized include acryloylmorpholinemorpholinomethylacrylamide (1)-vinyl-2-methylimidazole ethoxymethylacrylamide 1-vinyl-pyrrolidin-5-one. However, it is not limited to this.

(n) Here Z is ■ or C0NRsRa shows.

Fifth, aromatic phenols represented by the following general formula (IIr) or derivatives thereof can be used.

General formula (III) However, R31 represents H1 an alkyl group having 1 to 5 carbon atoms or -OH, and R3□ is H, -OH or COOH
represents.

Such compounds include phenol, catechol,
Examples include prologlucinol, salicylic acid, 3.5 dioxybenzoic acid, and pt-butylphenol.

Each of the above organic precipitants may be used alone or in two or more types.
Each group may be used in combination.

The above organic precipitant is added at the time of emulsion preparation, and
Sedimentation is caused by adjusting H, the by-product soluble salts are removed by discarding the supernatant, the precipitate is washed with water, and then, if necessary, in addition to gelatin, a method known to those skilled in the art is used. By adding sensitizers such as various sulfur sensitizers and gold sensitizers and heating and stirring to perform redispersion and chemical sensitization, the high contrast agent is used in the silver halide light-sensitive material of the present invention. Suitable contrast enhancing agents include tetrazolium compounds, and specific examples of tetrazolium compounds include those represented by the general formulas [T,], [T2], and [T3] described in JP-A-62-11253. It is possible to list compounds that are

[T3] In the formula, R5, R7, Ra, R9+R+2. R13, R+4
and R15 are each an alkyl group (e.g. methyl group, ethyl group, propyl group, dodecyl group, etc.), an allyl group, a phenyl group (e.g. phenyl group, tolyl group, hydroquinphenyl group, carboquinophenyl group, aminophenyl group, mercapto group) phenyl group, methoxyphenyl group, etc.), naphthyl group (e.g. σ-7tyl group, β-naphthyl group, hydroquine naphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.), and heterocyclic group (e.g. thiazolyl group, benzothiazolyl group) , oxacylyl group, pyrimidinyl group, pyridyl group, etc.), and any of these may be a group that forms a metal chelate or a complex. R
6 to R1o and R1+ are allyl group, phenyl group, naphthyl group, heterocyclic group, alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, mercaptomedel group, mercaptoethyl group, etc.), hydroxyl group, alkyl group Phenyl group, alkoxycarbonyl group, carboxyl group or its salt, carboxyl alkyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), amino group (e.g. amine group, ethylamino group, anilino group, etc.), mercapto group,
Represents a group selected from a nitro group and a hydrogen atom, and D is 2
E represents a group selected from an alkylene group, an arylene group, and an aralalkylene group, Xe represents an anion, and n represents 1 or 2. However, when the compound forms an inner salt, n is 1.

Next, specific examples of the cation moiety of the tetrazolium compound used in the present invention will be shown, but the cation moiety of the compound that can be used in the present invention is not necessarily limited to these.

(T-], ) 2-(benzodeazol-2-yl)
-3phenyl-5-dodecyl-2H-tetrazolium (T-2) 2.3-diphenyl-5-(4-t-
octyloquinphenyl)-2H-tetrazolium (T
-3) 2,3.54 rifhenyl-2H-tetrazolium (T-4) 2,3.5-)su(p-carboxyethylphenyl)-2H-tetrazolium (T-5) 2-(benzothiazol-2-yl )
-37 enyl 5-(0-chlorphenyl)-2H
-Tetrazolium (T-6) 2.3-diphenyl-2H-tetrathulium (T-7) 2.3-diphenyl-5-methyl-2
H tetrazolium (T-8) 3-(p-hydroquinphenyl)-
5-Methyl-2-phenyl-2H-tetrazolium (
T-9) 2.3-diphenyl-5-ethyl-2H
Tetrazolium (T-10) 2,3-diphenyl-5-n-hexyl 2H-tetrazolium (T-11) 5-cyano-2,3-diphenyl-
2HI3 Tetrazolium (T-12) 2-(benzothiazol-2-yl)-57enyl-3-(4-tolyl)-2H-tetrazolium (T-13) 2-(benzothiazol-2-yl)-5-( 4-chlorophenyl)-3-(4-nitrophenyl)2H-tetrazolium (T-14) 5-ethoxycarbonyl-2,3-
Di(3nitrophenyl)-2H-tetrazolium (T
-15) 5-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium (T-16) 2.5-diphenyl-3-(p-tolyl)2H-tetrazolium (T17) 2.5- Diphenyl-3-(p-iodophenyl)2H-tetrazolium (T-18) 2.3-diphenyl-5-(p-diphenyl)-2H-tetrazolium (T-19) 5-(p-bromophenyl)-2
-Phenyl-3-(2,4,6-)lychlorphenyl)-2I]-tetrazolium(T-20) 3-(p-hydroxyphenyl)-5-(pnitrophenyl)-2-phenyl-2
H-tetrazolium (T-21) 5-(3,4-dimethoxyphenyl)-3(2-ethoxyphenyl)-2-(4-methoxyphenyl)-2H-tetrazolium (T-22) 5-(4-cyano phenyl)-2,
3-diphenyl-2H-tetrazolium (T-23) 3-(p-acetamidophenyl)-2゜5-diphenyl-2H-tetrazolium (T
-24) 5-acetyl-2,3-diphenyl-
2H-Tetrazolium (T-25) 5-(Flu-2yl)-2,3-diphenyl-2H-tetrazolium (T-26) 5-(Flu-2yl)-2,3-
Diphenyl-2H-tetrazolium (T-27) 2.3-diphenyl-5-(pyrid-4yl)-2H-tetrazolium (T-28) 2.3-diphenyl-5-(quinol-2yl)-2H- Tetrazolium (T-29) 2.3-diphenyl-5-(penzoxazol-2yl)-2H-tetrazolium ('l
-30) 2.3-diphenyl-5-nitro 2H
Tetrazolium (T-31) 2.2',3.3'-tetraphenyl-5゜5'-14-butylene-diC2H-tetrazolium) (T-32) 2.2',3.3'-tetraphenyl -5゜5'-p-phenylene di(2
H-tetrazolium) (T-33) 2-(4,5-
dimethylthiazol-2yl)-3,5-diphenyl-2H-tetrazolium (T-34) 3,5-diphenyl-2-(triazin2yl-2H-tetrazolium) (T-35) 2-(benzothiazole-2 )
-3-(4methoxyphenyl)-5-phenyl-2
H-tetrazolium (T-36) 2,3-dimethoxyphenyl-5-
Phenyl-2H-tetrazolium (T-37) 2,3.5-)lis(methoxyphenyl)2H-tetrazolium (T-38) 2,3-dimethylphenyl-5-phenyl-2H-tetrazolium (T-39) 2.3-and droxyethyl-5-phenyl-2H-tetrazolium (T-40) 2.3-hydroxymethyl-5-phenyl-2H-tetrazolium (T'-41) 2.3-cyanohydroxyphenyl-5-phenyl- 2H-tetrazolium (T-42) 2.3-di(p-chlorophenyl)-
5-7enyl-2H-tetrazolium (T-43) 2,3-di(hydroxyethoxy7phere)-5-phenyl-2H-tetrazolium (T-4
4) 2.3-di(2-pyridyl)-5-7enyl-2H-tetrazolium (T-45) 2,3.5-)lis(2-pyridyl)
-2I-1 Tetrazolium (T-46) 2,3.5-) Lis(4-pyridyl)
-2H Tetrazolium When using a tetrazolium compound as a non-diffusible compound, a non-diffusible compound obtained by appropriately selecting a cation moiety and an anion moiety is used]9.

Examples of the anion moiety of the tetrazolium compound used in the present invention include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as sulfuric acid, nitric acid, and perchloric acid, sulfonic acid,
Acid groups of organic acids such as carboxylic acids, lower alkylbenzenesulfonic acid anions such as toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, higher alkyl sulfate ester anions such as lauryl sulfate anions, Dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxysulfate anions, higher fatty acid anions such as stearate anions, and acid groups in polymers such as polyacrylate anions. Examples include those with a .

By appropriately selecting the anion moiety and the cation moiety, the non-diffusible tetrazolium compound according to the present invention can be synthesized. The compound according to the present invention synthesized in this way is, for example, 2°3.5-triphenyl-2H-tetrazolium-dioctylsuccinate sulfonate, and after dispersing each soluble salt in gelatin, both In some cases, the oxidizing agent is mixed and dispersed in the gelatin matrix, and in other cases, crystals of the oxidizing agent are synthesized pure, dissolved in a suitable solvent (for example, dimethyl sulfoxide), and then dispersed in the gelatin matrix. If it is difficult to achieve uniform dispersion, emulsification and dispersion using an appropriate homogenizer such as ultrasonic waves or a Manton-Gorlin homogenizer may give good results. It is also possible to microdisperse it in a high boiling point solvent such as dioctyl phthalate, protect it, and then disperse it in a hydrophilic colloid layer.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional /SS silver lorane emulsions such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc. Any silver chloride used can be used, preferably silver chlorobromide containing 50 mol % or more of silver chloride as a negative-working mercury halide emulsion.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method. The silver halide emulsion used in the present invention may have a single composition, or may contain grains of a plurality of different compositions in a single layer or in a plurality of layers.

Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having (1001 plane) as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr, scυ 2)
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 1.39 (1973) and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Furthermore, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodispersed emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the silver halide weight contained within a grain size range of ±20% around the average grain size F is 60% or more of the total silver halide grain weight. It is preferably at least 70%, particularly preferably at least 70%, even more preferably at least 80%.

Here, the average particle size r is the particle size r when the product ni
Define 1.

(3 significant digits, minimum 4 to 5 decimal places.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the diameter in the case of grains with shapes other than spherical. This is the diameter when the projected image is converted into a circular image with a circumferential area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodispersed emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less. belongs to.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above.

Monodispersed emulsions are disclosed in JP-A-54-48521 and JP-A-58-49.
It can be obtained by referring to No. 938 and No. 60-122935.

Although the photosensitive silver halide emulsion can be used as a so-called unripe (Pr1mltive) emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
The book by Elikman et al. or the book by H. Fr1eser,
Die
Grundlagen der Photography
ischen Prozesse mit Silbe
rhalogeniden, Akademische
Verlagsgesellschaf [, 1968
) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat. , No. 2,278,947, No. 2
, No. 728, 668, 3, 656.

No. 955. As a reduction sensitizer,
Tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat.
No. 419,974, No. 2,518,698, No. 2,9
83゜609, 2,983,610, 2,69
No. 4,637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used. Specific examples thereof include U.S. Pat. 448,06
No. 0, British Patent No. 618.061, etc.

In addition, there are no particular restrictions on the conditions such as pHSpAg and temperature during chemical sensitization, but the pH value is preferably 4 to 9, especially 5 to 8, and the pAg value is preferably maintained at 5 to IL, especially 8 to 10. preferable. Also, the temperature is 40 to 90°C, especially 4
5-75°C is preferred.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.

In the silver halide photographic material according to the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex anine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, and the like. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus,
Quinoline nuclei etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. can be applied.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. About 1 OX 10-5 to about 5 X 10 of sensitizing dye per mole of silver halide
-' moles are preferred, particularly at concentrations of about 4.times.10@-' to 2.times.10@1 moles of sensitizing dye per mole of silver genide.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. More specific examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat. No. 2,519,001, No. 2
, No. 912, 329, No. 3,656゜956, No. 3,
No. 672,897, No. 3,694,217, No. 4.0
No. 25゜349, No. 4,046,572, British Patent 1
, No. 242,588, Special Publication No. 44-14030, No. 5
No. 2-24844, JP-A-48-73137, JP-A No. 61
-172140 etc. can be mentioned. As sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 945.763, British Patent No. 505,979, and Japanese Patent Publication No. 48-42172. Furthermore, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
, 270.378, 2,442,710, 2,
No. 454,629, No. 2,776.280, Special Publication No. 4
No. 9-17725, JP-A-50-62425, JP-A No. 61
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 29836 and No. 60-80841.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Typical examples are U.S. Pat. No. 2,688,545;
No. 977.229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527゜641, No. 3,61
No. 7,293, No. 3,628,964, No. 3,666
゜480, 3,672,898, 3,679,
No. 428, No. 3,703゜377, No. 3,769,3
No. 01, No. 3,814,609, No. 3,837°86
No. 2, No. 4,026,707, British Patent No. 1,344,
No. 281, No. 1,507,803, Special Publication No. 43-49
No. 36, No. 53-12375, JP-A No. 52-1106
No. 18, No. 52-109925, etc.

The silver halide photographic material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyania'PM, cyanine dyes, azo dyes, and the like. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles,
benzimidazoles (particularly nitro- or halogen-substituted), he-1+7ty ring mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly l-7 mercapto pyridines, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy Many compounds known as stabilizers can be added, such as substituted (1,3,3a,7)tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is in The Theory of the Photographic Process, by K. Mees.
Theory of the Photography
ic Process, 3rd edition, 1966), citing the original literature.

For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474 and U.S. Pat.
No. 947, No. 4,021,248 or Special Publication No. 1972-
The description in No. 28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, Special Publication No. 45-15462, Belgian Patent No. 7
62,833, U.S. Patent No. 3,767.410, Belgian Patent No. 558.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. As a hardening agent, aldehyde-based , epoxy-based, ethyleneimine-based, active halogen-based, hynylsulfone-based, isocyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, acyloyl-based hardeners, and ultraviolet absorbers include, for example, U.S. Pat. No. 253,921, British Patent No. 1,309,349, etc., especially 2-(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2
-(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-
3'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'
, 5'-di-tert-butylphenyl)-chlorobenzotriazole, and the like. Furthermore, British Patent No. 548.5 describes coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials.
No. 32, same 1. , 216,389, U.S. Pat. No. 2,02
No. 6,202, No. 3,514,293, Special Publication No. 1977-
No. 26580, No. 43-17922, No. 43-179
No. 26, No. 43-13166, No. 48-20785, French Painting Patent No. 202,588, Belgian Patent No. 773,
459, JP-A-48-101.118, etc., anionic, cationic, nonionic, or amphoteric compounds can be used, but among these, anionic surfactants having a sulfonic group are particularly suitable. Agents such as succinic acid ester sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, and the like are preferred.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
JP-A-48-89979, U.S. Patent No. 2,882,15
No. 7, No. 2,972.535, Japanese Unexamined Patent Publication No. 48-2078
No. 5, No. 48-43130, No. 48-90391,
There are compounds described in Japanese Patent Publications Nos. 46-24159, 46-39312, 48-43809, and 47-33627.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.3 to 7.
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that the pt+ of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is in the above range of 5.3 to 7.5. If the pH is less than 5.3, the progress of hardening is undesirable, and if the pH is greater than 7.5, it is undesirable because it adversely affects photographic performance.

In the light-sensitive material of the present invention, the constituent layers include matting agents such as silica described in Swiss Patent No. 330, 158, glass powder described in French Painting Patent No. 1,296,995, and glass powder described in British Patent No. 1,173,181. inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; starch described in U.S. Pat. No. 2,322,037, Berbeau Patent No. 6
Starch derivatives described in No. 25,451 or British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, and US patent Organic particles such as polyacrylonitrile as described in US Pat. No. 3,079,257 and polycarbonate as described in US Pat. No. 3,022,169 can be included.

In the photosensitive material of the present invention, the constituent layers include slipping agents, such as those described in US Pat. No. 2,588,756 and US Pat.
higher alcohol esters of higher aliphatics as described in U.S. Patent No. 3,295,979, higher aliphatic calcium salts as described in British Patent No. , U.S. Patent No. 3,042
, No. 522, and No. 3,489,567.

Dispersions of liquid paraffin and the like can also be used for this purpose.

Filter dyes or dyes used for irradiation prevention and other purposes include oxanol dyes,
Contains hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include West German Patent No. 616°007, British Patent No. 584,609,
No. 117,429, Special Publication No. 26-7777, No. 39-
No. 22069, No. 54-38129, Japanese Unexamined Patent Publication No. 1983-8
No. 5130, No. 49-99620, No. 49-1144
No. 20, No. 49-129537, No. 50-28827
No. 52-108115, No. 57-185038, U.S. Patent No. 1,878,961, No. 1884035
No. 1,912,797, No. 2,098,891, No. 2゜150.695, No. 2,274,782,
2,298.731, 2゜409.612, 2,461.484, 2,527,583, 2
No. 533.472, No. 2,865,752, No. 2,
No. 956,879, No. 3゜094.418, No. 3.1
No. 25,448, No. 3,148, No. 1.87, No. 317
No. 7078, No. 3,247,127, No. 3,260.
6 old number, 3゜282.699, 3,409,43
No. 3, No. 3,540,887, No. 3゜575.704
No. 3,653,905, No. 3,718,472, No. 3゜865.817, No. 4,070,352,
No. 4,071,312, PB Report No. 74175,
Photographic Abstract (Photo,
Abstr, ) 1 28 ('21), etc.

As the optical brightener, stilbene-based, triazine-based, pyrazoline-based, coumarin-based, and acetylene-based optical brighteners can be preferably used.

These compounds may be water-soluble, or insoluble ones may be used in the form of a dispersion.

Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-alkyl taurines, and Acid esters, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., containing acidic groups such as carboxyne groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. is preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides.

Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings are preferred.

Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene Glycol alkyl ethers, polyalkylene glycol alkyl amines or amides,
Preferred are polyethylene oxide adducts of silicone), glyceed derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and the like.

As a cloak agent, British patent No. 1,055,713,
U.S. Patent No. 1,939,213, U.S. Patent No. 2,221,873
No. 2,268,662, No. 2,332,037, No. 2,376.005, No. 2,391,181,
No. 2,701,245, No. 2,992,101, No. 3.079257, No. 3,262,782, No. 3,
No. 516,832, No. 3,539゜344, No. 3,5
No. 91,379, No. 3,754,924, No. 3,76
7゜448 etc., West German Patent No. 2,592.321, British Patent No. 760,775,
No. 1,260,772, U.S. Patent No. 1,201,905
No. 2,192,241, No. 3053.662,
No. 3,062,649, No. 3,257,206, No. 3322.555, No. 3,353,958, No. 3,
No. 370,951, No. 3゜411.907, No. 3,4
No. 37,484, No. 3,523,022, No. 3゜61
5.554, 3,635,714, 3,769
, No. 020, No. 4゜021.245, No. 4,029,
Inorganic mantle agents described in No. 504 and the like can be preferably used.

As an antistatic agent, British Patent No. 1,466.600,
Research Disclosure
Disclosure) No. 15840, No. 16258
No. 16630, U.S. Patent No. 2,327,828,
No. 2,861,056, No. 3,206,312, No. 3,245,833, No. 3,428,451, No. 3
, No. 775.126, No. 3,963,498, No. 4,
025. ．． No. 342, No. 4,025,4603, No. 4
, No. 025,691, No. 4,025,704, etc. can be preferably used.

Particularly preferred as an embodiment of the present invention is JP-A-62-
210458, JP-A No. 62-139546, and the like, a tetrazolium compound, a polyethylene oxide derivative, a phosphorus quaternary salt compound, a hydrazine compound, or the like is used as a tone control agent that promotes high contrast.

Further, it is also possible to use a technique in which a polymer latex is contained in a silver halide emulsion layer or a backing layer to improve dimensional stability. These techniques, for example,
No. -4272, No. 39-17702, No. 43-1.3
482, U.S. Patent No. 2,376.005, U.S. Patent No. 2,76
No. 3,625, No. 2,772.166, No. 2,852
, No. 386, No. 2,853,457, No. 3,397,
No. 988, etc.

Gelatin is used as the binder for the photosensitive material used in the present invention, but gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolymers, etc. Hydrophilic colloids such as synthetic hydrophilic polymer substances can also be used in combination.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bulletin on Society on Japan (Bull, Soc, Sci, Phot, Ja
Oxygen-treated gelatin as described in Pan) No. 16, page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesaltones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The product obtained by reacting is used. Specific examples are U.S. Pat. Nos. 2,614,928 and 3,132.
, No. 945, No. 3,186,846, No. 3,312,
553, British Patent No. 861,414, British Patent No. 1,033,
No. 189, No. 1,005,784, Special Publication No. 1972-26
It is described in No. 845, etc.

Proteins such as albumin and casein, cellulose derivatives such as hydroxy, diethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, and sugar derivatives such as sodium alginate and starch derivatives may be used in combination with gelatin.

The graft polymer of gelatin and other polymers includes gelatin and derivatives such as acrylic acid, methacrylic acid, their esters and amides, and single (homo) or copolymers of vinyl monomers such as acrylonitrile and styrene. A grafted material can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
No. 63,625, No. 2,831,767, No. 2956
It is described in No. 884, etc.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176 I tem
17643 (December 1978) and volume 187■t
em18716 (November 1979), and the relevant parts are summarized in the table below.

Supports used in the photosensitive material of the present invention include paper laminated with α-olefin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymers), visible reflective supports such as synthetic paper, cellulose acetate, etc. , cellulose nitrate1. Examples include films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports prepared by providing reflective layers on these films, and metals.

Among them, polyethylene terephthalate-1 is particularly preferred.

As the undercoat layer that can be used in the present invention,
Undercoating layer using organic solvent containing polyhydroxybenzenes as described in No. 9-3972, JP-A-4911118, JP-A No. 52-104913, JP-A No. 59-19941, JP-A No. 59-19940, JP-A No. 59-18945 No. 51-
No. 112326, No. 51-117617, No. 51-5
No. 8469, No. 51-114120, No. 51-121
No. 323, No. 51-123139, No. 51-1141
No. 21, No. 52-139320, No. 52-65422
Examples include water-based latex subbing layers described in Japanese Patent Application No. 52-109923, Japanese Patent No. 52-119919, Japanese Japanese Patent No. 55-65949, Japanese Japanese Patent No. 57-128332, and Japanese Japanese Patent No. 59-19941.

Further, the surface of the undercoat layer can usually be chemically or physically treated. Such treatments include surface activation treatments such as chemical treatment, mechanical treatment, corona discharge, electric treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, mixed acid treatment, and oson oxidation treatment. Can be mentioned.

The undercoat layer is distinguished from the coating layer according to the present invention, and there are no restrictions on the coating timing or conditions.

In the present invention, dyes can be used as filter dyes or dyes for various purposes such as preventing halation.

Dyes that can be used include triallyl dyes, oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes: hemioxanol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include West German Patent No. 616,007, British Patent No. 584.609,
No. 1.177429, Special Publication No. 1.17777, No. 3
No. 9-22069, No. 54-38129, Japanese Unexamined Patent Publication No. 1973
-85130, 49-99620, 49-11
No. 4420, No. 49-129537, No. 50-288
No. 27, No. 52-108115, No. 57-18503
No. 8, No. 59-24845, U.S. Patent No. 1,878,9
No. 61, No. 1,884,035, No. 1,912,79
No. 7, No. 2,098,891, No. 2,150,695
No. 2,274,782, No. 2,298,731
No. 2,409,612, No. 2,461,484, No. 2,527,583, No. 2,533,472,
2,865.752, 2,956,879, 3,094,418, 3,125.448, 3
, No. 148,187, No. 3,177.078, No. 3,
No. 247,127, No. 3,260,601, No. 3,2
No. 82.699, No. 3,409,433, No. 3,54
No. 0,887, No. 3,575,704, No. 3,653
, No. 905, No. 3,718,472, No. 3,865,
No. 817, No. 4,070,352, No. 4,071,3
No. 12, PB Report No. 74175, Photographic Abstract (Photo, Abstr,)
128 ('21) etc.

In particular, it is suitable to use these dyes in light-sensitive materials that have a sensitivity of 360 nm to 400 nm light.
It is particularly preferable to use it so that the sensitivity to nm light is 30 times or more higher.

Furthermore, when carrying out the present invention, Japanese Patent Application Laid-Open No. 61-26041
It is also possible to use an organic desensitizer in which the sum of the anode potential and the cathode potential of a polarograph is positive, as described in No. 1, etc.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the subfield range to which the emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenonark lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, Any known light source can be used, such as light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. Also, JP-A-62
-210458 and other UV light sources may be equipped with an absorption filter that absorbs wavelengths of 370 nm or less, or the emission wavelength may be reduced to 3
Preferable results can also be obtained by using a UV light source whose main wavelength is 70 to 420 nm.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, the 100 nanosecond to 1 microsecond exposure time using a cathode ray tube or xenon flash tube. It is also possible to provide exposures longer than 1 second. These exposures may be performed continuously or intermittently.

The present invention can be applied to various photosensitive materials such as printing, X-ray, general negative, general reversal, general positive, direct positive, etc., but extremely high dimensional stability is required. Particularly remarkable effects can be obtained when applied to photosensitive materials for printing.

In the present invention, various types of development processing such as black and white, color, and reversal processing using known methods can be used to develop the photosensitive material, but it is particularly effective when processing for printing photosensitive materials that provide high contrast. It is.

In the present invention, fixing solutions that can be used during processing include thiosulfates, sulfites, various acids, salts, fixing accelerators, wetting agents, surfactants, chelating agents, hardeners, etc. can be contained.

For example, thiosulfates and sulfites include the potassium, sodium, and ammonium salts of these acids; acids include sulfuric acid, hydrochloric acid, nitric acid, halic acid, formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid; Examples include citric acid, malic acid, phthalic acid, etc. Salts include potassium,
Examples include salts such as sodium and ammonium. . As the fixing accelerator, Japanese Patent Publication No. 45-35754, Japanese Patent Application Laid-open No. 5
Thiourea derivatives described in No. 8-122535 and No. 58-122536, alcohols having a triple bond in the molecule,
Examples include thioethers described in US Pat. No. 4,126,459, cyclodextran ethers that free anions, crown ethers, diazabicycloundecene, and di(hydroxyethyl)butamine. Examples of wetting agents include alkanolamine alcohols and the like. Examples of chelating agents include amine acetic acids such as nitrilotriacetic acid and EDTA. As a hardening agent, chromium alum, potassium alum, Aff compounds, etc. can be contained.

In the present invention, the fixer preferably contains an AQ compound in order to improve the hardness of the photosensitive material, and the content thereof is 0.1 to 3 g/Q in terms of AQ in the solution used. It is more preferable when

The preferred concentration of sulfite contained in the fixer is 0.03 to 0.
The amount is 4 mol/Q, more preferably 0.04 to 0.3 mol/Q.

The pH of the fixer is preferably 3.9 to 6.5.
i(), the fixing solution provides favorable photographic performance, and the effect of the packaging material of the present invention becomes remarkable.The most preferable pH of the solution is 4.2 to 5.3.

〔Example〕

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

Example I [Method for Preparing Emulsion] A silver chlorobromide emulsion was prepared using the following solutions A, B, and C.

Solution A> Ossein gelatin 170g polyisopropylene-polyethylene oxydisuccinic acid ester sodium salt 10% ethanol aqueous solution 50+nQ distilled water 12800m (1
Solution B> Silver nitrate 1700g Distilled water 4100mQ <Solution C> Sodium chloride 450g Potassium bromide 274g Polyisopropylene oxydisuccinate sodium salt 10% ethanol solution 3Qm (2 Ossein gelatin 1 10g Distilled water
4070 mO solution A was kept warm in 4 solution C, and JP-A No. 57-92523 and No. 57925
Solution B and solution C were added by the double jet method using the mixer described in No. 24.

As shown in Table 1, the addition flow rate was gradually increased over a total addition time of 80 minutes to form silver halide. During the first 5 minutes of mixing, the EAg of the emulsion was adjusted to 160
5 minutes after the start of mixing, the EAg value was changed to 120 mV using a 3 mol/a aqueous sodium chloride solution, and this value was maintained thereafter until the completion of mixing.

To keep the EAg value constant, a metal silver electrode and a double junction saturated Ag/Ag (J2 reference electrode) were used to measure the EAg value. The double junction disclosed in Japanese Patent Publication No. 197534/1986 was 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 pn value of the system was kept constant at 3.0.
% nitric acid aqueous solution.

After addition of liquids B and C, the emulsion is subjected to Ostwald ripening for 10 minutes. This emulsion was divided into five parts, each of which was subjected to aggregation, drainage, and water washing three times using a 5% solution of naphtholsulfonic acid acetaldehyde resin (average degree of condensation of about 5, bound sulfuric acid 30% by weight), and then 120% of an aqueous solution of ossein gelatin.
Add 0m0 (containing 60g of ossein gelatin) and
The pH was adjusted to 5.8 with a 6% aqueous sodium carbonate solution or a 6% HNO3 solution, and the mixture was dispersed by stirring at 55° C. for 30 minutes, and then adjusted to 15,000 cc.

The finished emulsions were adjusted so that the residual amount of the naphtholsulfonic acid acetaldehyde resin was as shown in Table 2. The degree of sedimentation was adjusted by adjusting the pn level.

It should be noted that emulsions with a residual amount of 0.1 g or less per mole of silver halide have poor settling properties.

The average grain size of the silver chlorobromide grains contained in the obtained emulsion was 0.
, 20 μm, and 85% of the total number of particles have a particle size of 0.14-0.
26 μm Table 2 Residual amount of naphtholsulfonic acid acetaldehyde resin (number of grams per mole of silver halide) Sensitizing dye A CH2CHiCN Sensitizing dye B The residual amount was measured by spectroscopic absorption method, Shimadzu spectrofluorescent instrument RF-5
30 was used.

The remaining amount of emulsion A is outside the scope of the present invention.

The obtained emulsions (A) to (E) were each subjected to total sulfur sensitization, and 300 mg of sensitizing dye A was added per mole of silver halide contained in the emulsion, and 4-hydroxy-6- was added as a stabilizer. Add 1 g of methyl-1,3,3a,7-titrazaindene, add sensitizing dye B to the emulsion, add 800 mg of the tetrazolium compound shown in T-36 per mole of silver halide, and add p-dodecylbenzenesulfonic acid. 300 mg of soda, 2 g of styrene-maleic acid copolymer, styrene-butyl acrylate-acrylic acid copolymer latex (average particle size approximately 0.25 μm) 1
5 g was added, and the amount of Ag and gelatin were as shown in Table 2, and the coating was applied onto a subbed polyethylene terephthalate film base as described in Example (1) of JP-A-59-19941. At that time, the amount of gelatin is as shown in Table 3.
A protective layer containing 10+ng/m'' of bis-(2-ethylhexyl)sulfosuccinic acid ester as an agent, 15 mg/m2 of formalin and 8 mg/m2 of glyoxal as a hardening agent was simultaneously coated.

Samples Nos. 1 to 29 were prepared with the configurations shown in Table 3, and the following evaluations were performed. The results are shown in Table 4.

The samples in Table 3 were exposed to light using a tungsten light source using a wedge and developed. The development process was carried out using the developer and conditions shown below. The amount of silver was analyzed using a fluorescent X-ray analyzer. However, the amount of silver after treatment is expressed as the amount of silver that gives the maximum density.

Measurement of Pressure Resistance Regarding pressure resistance, after 95% of these samples were photographed, the exposed samples were bent under a constant pressure and developed. Those with a large concentration change due to pressurization are ranked 11, and those with no concentration change are ranked 10.
A graded evaluation was performed.

Rank 4 is a level that poses a problem in practice.

Development processing conditions> (Process) (Temperature) (Time), (Capacity)
Image 35°O 15 seconds 20Q constant
Wash at 35°O for 15 seconds with 20M water
18°C 10 seconds 1512 drying
40°0 10 seconds Each process also includes the so-called wading conveyance time until the next process. Dry to Dry time is 50 seconds.

The results are shown in Table 3.

Developer formulation> (Composition A) Pure water (ion exchange water) 150n+Q
Polyethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50g Potassium sulfite (55% W aqueous solution) loOm (Potassium 1 carbonate 50g Hydroquinone
15g 5-Methylbenzotriazole 200mg 1-7enyl-5-mercaptotetrazole 0mg Potassium hydroxide Amount to bring the pH of the working solution to 1004 Potassium bromide 4.5g (composition) Pure water (ion-exchanged water) 3m12 Diethylene glycol 50g Ethylenediaminetetraacetic acid 2 Sodium salt 5mg Acetic acid (90% aqueous solution) 0.3mff
5-Nitroindazole 110mg1-
7x Neal-3-pyrazolidone 700mg Butylamine diethanolamine 15g Water 5 when using developer
Dissolve the above composition A in the order of composition A and IQ
It was finished and used.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0m (2 Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate,
2g acetic acid (90% w/v aqueous solution)
13.6m (1 (composition) Pure water (ion exchange water) 17m12 Sulfuric acid (50% w/w aqueous solution) 4.7g aluminum sulfate (aqueous solution with AQ203 equivalent content of 8.1% w/w) 26
．． When using 5 g of fixer, the above compositions were dissolved in 500 m of water (2) in the order of composition A and composition and finished to H. This constant gamma is defined for a density of 0.3 to 3.0.

If the gamma is less than 5, the fine lines will be crushed and it will be difficult to put it into practical use.

From the results in Table 4, it can be seen that the samples of the present invention have excellent contrast resistance and high contrast compared to the comparison.

Example 2 A similar experiment was conducted in Example 1 by replacing the tetrazolium compound (T-36) with the following compound, and the same results as in Example 1 were obtained.

〔Effect of the invention〕

The present invention provides excellent pressure resistance even in ultra-rapid processing.
It has been possible to provide a silver halide photographic material and a processing method thereof, in which silver in the material can be effectively developed and high-contrast images can be obtained.

Claims (3)

[Claims] (1) In a silver halide photographic light-sensitive material containing a silver halide emulsion obtained by coagulation and desalting with an organic precipitant,
The residual amount of the organic precipitant after desalting is 0.1 to 8.0 g per mole of silver halide, and the support of the silver halide photographic light-sensitive material includes a silver halide emulsion layer. A silver halide photographic material characterized in that the weight ratio of silver to gelatin in the hydrophilic colloid layer on the side is 1.0 or more. (2) A processing method comprising processing the silver halide photographic material according to claim 1 within a development time of 19 seconds. (3) A method for processing a silver halide photographic light-sensitive material according to claim 2, wherein the total processing time of Dry to Dry is 20 seconds to 60 seconds.