JPH0443339A - Silver halide photographic sensitive material improved in pressure resistance and processing method - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material which has the adaptability to ultra-rapid processing and is improved in pressure resistance by respectively specifying the residual amt. of an org. settling agent after desalting and the amt. of the latex polymer in hydrophilic colloidal layers on the side contg. emulsion layers with respect to a base. CONSTITUTION:This photosensitive material contains the silver halide emulsion obtd. by subjecting the emulsion to flocculation desalting by the org. settling agent. The residual amt. of the org. settling agent after the desalting is 0.1 to 8.0g per 1mol silver halide. In addition, the latex polymer is incorporated at 0.2 to 3.0g/m<2> into the hydrophilic colloidal layers on the side contg. the emulsion layers with respect to the base. The silver halide photographic sensitive material is processed within 19sec development processing time and the total dry to dry processing time is preferably 20 to 60 seconds. The excellent pressure resistance in the ultrarapid processing is obtd. in this way and the silver in the photosensitive material is effectively developed. In addition, high-contrast images are obtd.

Description

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

[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. On the other hand, in order to improve work ease and stability,
From so-called lithographic development, which has conventionally been commonly used in the development of printed photosensitive materials, rapid access development has come into use, which improves its shortcoming of stability.

In this case, by incorporating a high contrast agent such as a tetrazolium compound or a hydrazine compound into the silver halide emulsion, a high contrast equivalent to that of lithographic development can be achieved, and development can be performed in 20 to 30 seconds. However, the above-mentioned requirements further include a strong requirement for development time of 20 seconds or less, and of course, deterioration in image quality is not acceptable. On the other hand, in printing there is an operation called reduction, and therefore 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 which has excellent pressure resistance even in ultra-rapid processing, allows the silver in the light-sensitive material to be effectively developed, and provides high-contrast images. An object of the present invention is to provide a photosensitive material and a processing method.

[*Achievement of invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material containing a silver halide emulsion obtained by coagulation and desalting with an organic precipitant, in which the residual amount of the organic precipitant after desalting is 1 mole of silver halide. silver halide, characterized in that the latex polymer is 0.1 to 8.0 g per unit, and 0.2 to 1Og/■8 of a latex polymer is contained in the wood-philic colloid layer on the side containing the emulsion layer with respect to the support. The photographic light-sensitive material and the silver halide photographic light-sensitive material are processed within a development processing time of 19 seconds, and the total processing time of Dry to Dry is 20 seconds to 6 seconds.
This is achieved by being 0 seconds.

Detailed Description of the Present Invention In the present invention, Dry to Dry refers to the entire process from inserting the leading edge of a photosensitive material into an automatic developing machine, developing, fixing, washing with water, and drying until the leading edge emerges from the automatic developing machine. It's time. In other words, the total length of the processing line including the transition part of the multi-tank (■)
divided by the line conveyance speed (time/sec) (sec
), and is characterized in that the value is 60 seconds or less.

In addition, the amount of gelatin in the embodiment of the present invention refers to the total amount of gelatin in one or more layers on the side containing the photosensitive silver halide emulsion layer with respect to the support, and the amount of gelatin in the silver halide emulsion layer It is not limited. 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 90% silver halide monolayer I2. 1~
The weight is 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 t per mole of silver;
90.1 to 5.0 g, more preferably 0.1 to 5.0 g
3, Og.

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, using organic polymers or non-polymeric sulfonic acids or sulfuric acids that function as coagulants, such as 7tale disulfonic acid, polystyrene sulfonic acid and derivatives, long chain alkyl sulfonic acids and sulfuric acids, e.g. various anionic wetting agents. be able to.

Secondly, a sulf7onated product of 7-enoleanoledehyde St fat 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. An example of such a compound is a resin obtained by combining seven enols such as phenol, cresol, resolnon, and naphthol with aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde, and a resin obtained by combining 5 to 10 times the amount of concentrated acetate.
Examples include those obtained by heating with an acid or 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 degree of condensation have a narrow pH range in which the emulsion can coagulate and precipitate and are difficult to handle, and those with a high degree of condensation tend to be colored during resin production and have an excessive thickening effect, so generally the average degree of condensation is 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) CH, -CH Here 2 is or -CONHR' (R'1iCH20H.

-CH, OCR, -CH, QC, H, or fourthly,
A polymer of 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof (I) or a copolymer of (I) and a vinyl compound represented by the following general formula (I[) can be used.

General formula (I) CH.

i3 However, M is hydrogen, Li, Na, K, NH, Rl
+ represents Rx+R1, Rr, R! , Rs each represents an alkyl or substituted alkyl having 5 or less carbon atoms. However, R,,R,,
R.

The number of carbons in will not exceed the total IO.

Representative examples of 2-acrylamido-2-methylpropanesulfonic acid or its salts include: 2-acrylamido-2-methylpropanesulfone, potassium 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamido-2-methylpropanesulfonic acid. Examples include sodium ammonium 2-acrylamido-2-methylpropanesulfonate, triethylammonium 2-acrylamido-2-methylpropanesulfonate, and bishydroxymethylammonium 2-acrylamido-2-methylpropanesulfonate. However, it is not limited to this.

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 2 is or -CONR, R.

-CH2OCR3, -CH2QC, H, or.

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

General formula (II[) where R31 is H1 an alkyl group having 1 to 5 carbon atoms;
represents -OH, and R32 is! (, -OR or -C
Represents 0OH.

Such compounds include phenol, catechol,
Prologlucinol, salicylic acid, 3,5-dioxybenzoic acid, p-j-butylphenol, etc.

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. A silver halide emulsion can be obtained by adding sensitizers such as various sulfur sensitizers and gold sensitizers and heating and stirring to perform redispersion and chemical sensitization.

The latex polymer used in the present invention preferably contains (meth)acrylic acid polymer units. Examples of (meth)acrylic acid-based polymers include copolymers of (meth)acrylic acid, homopolymers of (meth)acrylic esters, copolymers of (meth)acrylic esters, and the like.

Specifically, a homopolymer of alkyl acrylate, a homopolymer of alkyl methacrylate, a homopolymer of alkyl acrylate, alkyl methacrylate, acrylate, methacrylate, and other ethylenically unsaturated polymerizable compounds. or one or more 100-C (preferably Ill or one or more C) 12-C<
Examples include water-insoluble addition polymers such as those having the following:

Specific examples of the above (meth)acrylic acid-based polymer include copolymers of acrylate and vinylidene chloride, copolymers of methacrylate and vinylidene chloride, copolymers of acrylate and vinyl esters, and copolymers of methacrylate and vinyl esters. Examples include copolymers of at least one compound selected from acrylic acid, methacrylic acid, and itafonic acid, and these copolymers are preferred.

Specific examples of acrylate and methacrylate include ethyl acrylate, n-butyl acrylate, n-
Octyl acrylate, n-dodecyl acrylate, ethyl methacrylate, n-butyl methacrylate, n
-octyl methacrylate, n-dodecyl methacrylate and the like. Specific examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl acetate, vinyl laurate, and the like. The molecular weight of the copolymer is practically preferably 500 to 500,000. Specific examples of such homopolymers or copolymers are shown below.
-1 to L-12, but are not limited to these homopolymers or copolymers.

homopolymer +CH2-CH+- COOC31 (+ M=lO million L-7 CH.

α)QC,H.

α phantom H 50,000 yen COOC, H.

α)OH M-200,000 C.B.

α)OCH3 OOH M Aya l O million CH.

x: y: z=70: 28 M-500,000 COOC, H.

a M=t160,000M#300,000x:y:z-80:16if)IQ10,000In addition, in the above L-1-L-12, x. y. z
is the mol% of each monomer component, and M is the average molecular weight (in this specification, average molecular weight refers to number average molecular weight)
represents.

Generally, the (meth)acrylic acid-based polymer has at least 65%, preferably 75 to 95% by weight of alkyl acrylate, alkyl methacrylate (e.g., ethyl acrylate, methyl acrylate, butyl acrylate, ethyl acrylate, octyl methacrylate, etc.). Preferably, polymers are used. In addition,
Polymers most useful in the practice of this invention generally have an average molecular weight of about 500 to about soo. ooo, and the particle diameter in the dispersion is generally 17,711 or less.

The above-mentioned (meth)acrylic acid-based polymer is insoluble in water, but it can be easily dispersed in water, and the above-mentioned (meth)
The meth)acrylic acid-based polymers can be mixed with suitable silver halide veptizers such as gelatin or mixtures with other photographic binders.

The amount of latex polymer contained in the silver halide photographic light-sensitive material of the present invention is 0.000000000000000000000000000000000000000000000000000000000000 type type type type type type type type type form nature form nature form type nature form type form.
It is preferable to add 1 g to 10 g, particularly preferably 0.2 g to 5 g.

Preferred examples of the contrast enhancing agent used in the present invention include tetrazolium compounds, and specific examples of tetrazolium compounds include general formulas (T)-11 (T)-2 and [T] described in JP-A-62-11253. -3 can be mentioned.

[T)-3 where Rs, Rr, Rs, R*, R+z, R13, R14
and R1° each represent 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, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group) group, methoxyphenyl group, etc.), naphthyl group (e.g. a-naphthyl group, β-naphthyl group, hydroxynaphthyl 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.

R6-R4° and R1 are allyl group, 7-enyl group, naphthyl group, heterocyclic group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, mercaptomethyl group, mercaptoethyl group, etc.) , hydroxyl represents a group selected from a group, a nitro group, and a hydrogen atom, and D
represents a divalent aromatic group, E represents a group selected from an alkylene group, an arylene group, and an aralalkylene group;
Q 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-1) 2-(benzothiazol-2-yl)
-3-722-5-dodecyl-2H-tetrazolium (T-2) 2,3-diphenyl-5-(4-t-
octyloxyphenyl)-2) 1-tetrazolium (
T -3') 2.3.5-Triphenyru 2H-
Tetrazolium (T-4) 2,3.5-tri(p-carboxyethyl7enyl)-2H-tetrazolium (T-5) 2-(benzothiazol-2-yl)
-3-722-ru5-(o-chlorphenyl)-2
H-tetrazolium (T-7)2,3-diphenyl-5-methyl-2H
-Tetrazolium (T-8) 3-(p-hydroquinphenyl)-
5-Methyl-2-phenyl-28-tetrazolium (
T-9) 2.3-diphenyl-5-ethyl-2
H-tetrazolium (T-10) 2.3-diphenyl-5-n-hexyl-2F+-tetrazolium (T-II) 5-noano2.3-diphenyl-21-tetrazolium (T-12) 2-(benzothiazole -2-yl)-5-722-ru-3-(4-tolyl)-2H-tetrazolium(T-13) 2-(benzothiazol-2-yl)-5-(4chlorophenyl)-3 -(4
-nitrophenyl) 2H-tetrazolium 14) 5-ethoxycarbonyl-2,3-di(3-nitrophenyl)-2H-tetrazolium (T (T -15) 5-acetyl-2,3-di(p-ethoxyphenyl) )-2H-tetrazolium (T-6) 2.3-diphenyl-2H-tetrazolium (T-16) 2.5-diphenyl-3
-(p-)yl)-2H-tetrazolium (T-17) 2,5-diphenyl-3-(p-
iodo7enyl) 28-tetrazolium (T-18) 2,3-diphenyl-5-(p-
diphenyl)-211-tetrazolium (T-19) 5-(p-bromophenyl)-2
-722-3-(2,4,6-1-lychlorphenyl)-2H-tetrazolium (T-20) 3-(p-hydroxyphenyl)-5-(p-nitrophenyl)-2-7enyl 2
H-tetrazolium (T-21) 5-(3,4-dimethoxyphenyl)-3-(2ethoxyphenyl)-2-(4-methoxyphenyl)-2H-tetrazolium (T-22) 5-(4- cyanophenyl)-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-(thieso-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-(benzoxazol-2yl)-2H-tetrazolium (T
-30) 2.3-diphenyl-5-nitro-2
H-tetrazolium (T-31) 2.2', 3.3'-tetraphenyl-5,5'-1°4-butylene-di(2H-tetrazolium) (T-32) 2.2', 3. 3'-
Tetraphenyl-5,5'-pphenylene di(2
H-tetrazolium) (T-33) 2-(4,5
-dimethylthiazol-2yl)-3,5-diphenyl-2H-tetrazolium (T-34) 3,5-diphenyl-2-(triazin-2yl-2H-tetrazolium) (T-35) 2-(benzothiazole -2il)
-3-(4-methoxyphenyl)-5-phenyl-
28-tetrazolium (T-36) 2.3-dimethoxyphenyl-5
-7 enyl 2H-tetrazolium (T -37) 2.3.5- Tris(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-5-7enyl-2H-tetrazolium (T-42) 2,3-di(p-chlorophenyl)
-5-phenyl-2H-tetrazolium (T -43) 2.3-di(hydroxyethoxyphenyl)-5-phenyl-28-tetrazolium (T
-44) 2.3-Di(2-pyridyl)-5-7enyl-2H tetrazolium (T-45) 2.3.5-) Lis(2-pyridyl)-2-day-tetrazolium (T-46) 2. 3.5- Tris(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.

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 p-toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, and 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 polyethenoxy sulfate anions, higher fatty acid anions such as stearate anions, and polymers such as polyacrylate anions. It is a good idea to list things that have acid roots.

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, dimethylsulfokind), 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. -Also finely dispersed in high boiling point solvents such as dioctyl phthalate,
It is also possible to protect it and disperse it in a hydrophilic colloid layer.

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

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 preferred example is a cube having the +1001 plane as the 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, Sci.
), 21.39 (1973), etc., particles having shapes such as octahedron, (1) tetrahedron, and (2) dihedron may be prepared 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.

Further, any grain size distribution may be used, and an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a jK branching emulsion). may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

In the present invention, monodisperse emulsions are preferred. Monodisperse silver halide grains in a monodisperse emulsion include 1:j&halogenated # within a grain size range of ±20% around the average grain size r.
! It is preferable that the weight is 60% or more of the total weight of the silver halide grains, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle diameter ``defines the particle diameter aperture when ffn1Xri3 between the frequency of particles having particle diameter ri and r[3 is maximum.

(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 the circumferential area of the circle IJ2.

The particle size can be obtained, for example, by photographing the particles with an electronic 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 particles to be measured shall be indiscriminately 1000 fi1 or more.) The particularly preferred highly dispersed emulsion of the present invention has a distribution width defined by 20% or less, more preferably 15% or less. It is something.

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 without chemical sensitization as a so-called prismatic emulsion, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
eliklan et al. or H. Frleser, ed.
Die
Grundlagen der Photography
ischen Prozesse sit Silbe
rhalogeniden, Akademische
Verlaggesellschaft, 196
The method described in 8) 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 include U.S. Pat. No. 689, No. 2,278,947,
It is described in No. 2,728,668 and No. 3,656°955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. ,97
No. 4, No. 2,518,698, No. 2,983°609
No. 2,983.610 and No. 2,694.637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group II of the periodic table, such as platinum, iridium, and palladium, can be used.
, No. 399,083, No. 2.448.060, British Patent No. 618.061, etc.

In addition, there are no particular restrictions on the conditions such as PH, PAg, temperature, etc. during chemical sensitization, but the pH value is preferably 4 to 9, especially 5 to 8, and the PAg value is 5 to 11, especially 8 to 10. It is preferable to keep it. Further, the temperature is preferably 40 to 90°C, particularly 45 to 75°C.

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, 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 emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or the emulsion may be left containing any unnecessary soluble salts. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure 1764:1.

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, melonanine dyes, complex cyanine dyes, complex mero/anine dyes, holobolanine dyes, hemi-7anine dyes, styryl dyes, hemioxonol dyes, and the like. Particularly useful pigments are pigments belonging to the Ayu 2 pigments, merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline 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, thiobarbital acid group, etc. can be applied.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in a normal negative silver halogenide emulsion. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion. About 1 OX 10-' to about 5 X 1 of sensitizing dye per mole of silver halide
0-' moles are preferred, especially concentrations of about 4.times.10-' to 2.times.10-' moles of sensitizing dye per mole of silver halide.

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 the sensitizing dye 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. Sensitizing dyes used in green-sensitive silver halide emulsions are described, for example, in US Pat.

No. 939.201, No. 2,072,908, No. 2,7
No. 39,149, No. 2945.763, British Patent No. 5
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent Publication No. 05,979 and Japanese Patent Publication No. 48-42172. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
No. 69,234, No. 2,270,378, No. 2,44
No. 2.710, No. 2,454.629, No. 2,776
．． No. 280, Japanese Patent Publication No. 17725-1972, Japanese Patent Publication No. 17725-
No. 62425, No. 61-29836, No. 60-808
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 41.

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
No. 480, No. 3,672.898, No. 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 light-sensitive 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/yellowation, and preventing airway formation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, mero/anine dyes, /anine dyes, azo dyes, and the like. Among these, oxonol dyes: hemioxonol dyes and mero/anine 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), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5
・Mercaptotetrazole), mercaptopyridines,
The above-mentioned heterocycles having water-soluble groups such as carboxyl groups and sulfone groups, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a
, 7) tetraazaintenes), benzenethiosulfonic acids, benzenesulfinic acids, etc., many compounds known as stabilizers can be added.

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. 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 type, ethyleneimine type, active halogen type, vinyl sulfone type, incyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, anroyl type, etc., and UV absorbers include, for example, US patents. No. 3,253,921, British Patent No. 1,309,349, etc. The compounds described herein, especially 2-(2'-hydroquine-5-tertiary) tylphenyl 2-(2'-hydroquine-3',5' -di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy/-3'-tert-butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di3 class butylphenyl 1
Examples include 5-chlorobenzotriazole. Furthermore, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent Nos. 548 and 532; No. 1.216.389,
U.S. Patent Nos. 2,026,202 and 3,514,293
No., Special Publication No. 44-26580, No. 43-17922, No. 43.17926, No. 43-13166, No. 4
No. 8-20785, French Patent No. 202.588, Belgian Patent No. 773,459, JP-A-48-101118
Anionic, cationic, nonionic or amphoteric compounds described in the above can be used, but among these, anionic surfactants having a sulfonic group, such as succinic acid ester sulfonates, alkylnaphthalenes, etc. can be used. Sulfonated compounds, alkylbenzene sulfonated compounds, and the like are preferred.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
JP 48-89979, U.S. Patent No. 2.882,15
No. 7, No. 2,972, No. 535, Japanese Unexamined Patent Publication No. 48-2078
No. 5, No. 48-43130, No. 48-90391,
There are compounds described in Japanese Patent Publication Nos. 46-24159, 46-39312, 4g-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 pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within 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 matte Ifl, such as silica described in Swiss Patent No. 330,158, glass powder described in French 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 such as cadmium, zinc; starch as described in U.S. Pat. No. 2,322,037, Belgian Patent No. 6
Starch derivatives described in No. 25,451 or British Patent No. 981.198, polyvinyl alcohol described in Japanese Patent Publication No. 3643/1983, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, and U.S. Pat. , 079,257, and polycarbonate described in US Pat. No. 3,022,169.

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. Pat. No. 3,295.979, casein as described in U.S. Pat. , 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. Pat. No. 1,878,961, Id.

No. 884.035, No. 1,912.797, No. 2,0
No. 98.891, No. 2゜150.695, No. 2,27
No. 4.782, No. 2.298.731, No. 2.409
．． No. 612, No. 2,461,484, No. 2,527.
No. 583, No. 2゜533.472, No. 2,865,7
No. 52, No. 2,956.879, No. 3°094.41
No. 8, No. 3,125,448, No. 3.148.187
No. 3゜177.078, No. 3,247.127, No. 3,260.601, No. 3゜282.699,
3,409.433, 3,540,887, 3゜575.704, 3,653,905, 3
, No. 718,472, No. 3865.817, No. 4,0
No. 70,352, 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 Those containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups, etc., such as acid esters, sulfoalkylpolyoquine ethylene alkylphenyl ethers, and polyquinoethylene alkyl phosphate esters. is preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric 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. etc. are preferred.

Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters,
Preferred are polyalkylene glycol alkylamines or amides, 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 matting agents, British Patent No. 1,055.713, U.S. Patent No. 1,939.213, U.S. Patent No. 2,221.873, U.S. Patent No. 2,268,662, U.S. Patent No. 2,332,037,
2,376.005, 2,391.181, 2,701.245, 2,992.101, 3
, 079°257, 3,262,782, 3,
No. 516.832, No. 3,539゜344, No. 3,5
No. 91.379, No. 3,754.924, No. 3, 7
67.

Organic matting agent described in No. 448 etc., West German patent 2
, No. 592,321, British Patent No. 760.775, No. 1
, 260.772, U.S. Pat. No. 1,201,905,
2.192.241, 3゜053.662, 3,062,649, 3,257,206, 3
゜322.555, 3,353,958, 3,
370.951, 3゜411.907, 3,4
37.484, 3,523.022, 3゜61
5.554, 3,635,714, 3,769
．． No. 020, No. 4゜021.245, No. 4,029.
Inorganic matting agents such as those described in No. 504 can be preferably used.

As an antistatic agent, British Patent No. 1,466.600,
Research Disclosure (i1636arch
Disc-1osure) No. 15840, No. 162
No. 58, 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,
Described in No. 3,775.126, No. 3,963,498, No. 4,025.342, No. 4,025.4603, No. 4,025,691, No. 4,025.704, etc. Compounds 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. 43-134
No. 82, U.S. Patent No. 2,376.005, U.S. Patent No. 2,763
, No. 625, No. 2,772.166, No. 2,852.
No. 386, No. 2,853,457, No. 3,397,9
It is described in No. 88, etc.

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

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bulletin on Society on Gisebang (Bull, Sac, 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. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent 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 include albumin and casein, and cellulose derivatives include hydroxyethylcellulose and calhoki/
Methyl cellulose, cellulose sulfate ester, or sugar derivatives such as sodium alginate and starch derivatives may be used in combination with gelatin.

The above-mentioned graft polymer of gelatin and other polymers may be a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. to gelatin. 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. Patent 2.7
No. 63.625, No. 2,831.767, No. 2,95
6.184 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 support used in the photosensitive material of the present invention includes a
Flexible reflective supports such as paper laminated with olefin polymers (e.g. polyethylene, polypropylene, ethylene/puden copolymer), synthetic paper, etc., cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide These include films made of semi-synthetic or synthetic polymers such as, flexible supports provided with reflective layers on these films, metals, and the like.

Among them, polyethylene terephthalate 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 the water-based latex subbing layer described in No. 52-109923, No. 52-119919, No. 55-65949, No. 57-128332, and No. 59-■9941.

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 geography, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. .

The undercoat layer is distinguished from the coating layer according to the present invention, and there are no restrictions on 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 may be used include triallyl dyes, oxanol dyes, hemioxanol dyes, mero/anine dyes, anine 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 are West German Patent No. 616.007, British Patent No. 584.609,
No. 1,177.429, Japanese Patent Publication No. 26-7777, No. 39-22069, No. 54-38129, Japanese Patent Publication No. 4
No. 8-85130, No. 49-99620, No. 49-1
No. 14420, No. 49-129537, No. 50-28
No. 827, No. 52-108115, No. 57-1850
No. 38, No. 59-24845, U.S. Patent No. 1.878.
No. 961, No. 1.184.035, No. 1,912.7
No. 97, No. 2,098,891, No. 2,150.69
No. 5, No. 2.274.782, No. 2,298,731
No. 2,409,612, No. 2,461,484, No. 2,527,583, No. 2,533,472,
No. 2,865,752, No. 2,956,879, No. 3,094.418, No. 3,125,448, No. 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, PR Report No. 74175, 7 Otograph (”
/ri・abs, tract (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 n-light.
It is particularly preferable to use it so that the sensitivity to n■ light is 30 times or more.

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 to electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (El light), tungsten lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, and 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, σ-rays, or the like. Also, Tokukai Sho 6
Even if a UV light source such as No. 2-210458 is equipped with an absorption filter that absorbs wavelengths of 370 nm or less, or a UV light source whose main emission wavelength is between 370 and 420 nm can produce favorable results. can get.

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 for printing, for X-ray, for general negatives, for general reversals, for general positives, and for direct positives, but extremely high 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 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, Examples of the acid include tartaric acid, citric acid, malic acid, heptatalic acid, and the like, and examples of the salt include potassium, sodium, and ammonium salts of these acids. 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, nclodextran ethers that free anions, crown ethers, diazavincloundecene, di(hydroquinethyl)butamine, and the like. Examples of wetting agents include alkanolamines and alkylene glycols. Examples of chelating agents include aminoacetic acids such as nitrilotriacetic acid and EDTA. As a hardening agent, in addition to chromium alum and potassium alum, ○ compounds and the like can be contained.

In the present invention, the fixer preferably contains an AI2 compound in order to improve the hardness of the photosensitive material, and when the content is 0.1 to 3 g/a in terms of A12 in the solution used, further preferable.

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 preferred pH of the fixer is 3.9 to 6.5;
The fixer gives favorable photographic performance, and the effect of the packaging material of the present invention becomes significant. The most preferable liquid pH is 4.
It is 2 to 5.3.

〔Example〕

The present invention will be explained in more detail by showing specific examples below. It should be noted that the present invention is not limited to the following examples.

Example 1 [Method for Preparing Emulsion (A)] A silver chlorobromide emulsion was prepared using the following solutions A, B, and C.

Solution A〉 Ossein gelatin 170g Polypropylene-polyethylene oxydisuccinate sodium salt 10% ethanol aqueous solution 50m<1 Distilled water 12800ml Solution B
〉 Silver nitrate 1700g distilled water
4100mQ (Solution C) Sodium chloride 450g Potassium bromide 274g Polyisopropylene oxydisuccinate ester-sodium salt 10% ethanol solution 30■Q Ossein gelatin 110g Distilled water
The 4070ml solution A was kept warm at 40°C, and JP-A No. 57-92523 and No. 57-9252 were prepared.
Solution B and solution C were added by a double jet method while stirring using a mixer described in No. 4.

As shown in Table 1, the addition flow rate was gradually increased over a total addition time of 80 minutes to form silver halide grains. During the first 5 minutes of mixing, the emulsion has an EAg value of 1.
The EAg value was maintained at 60 mV, and 5 minutes after the start of addition, the EAg value was changed to I20+*V using a 3 mol/a aqueous sodium chloride solution, and this value was maintained thereafter until the completion of mixing. In order to keep the EAg value constant, a metal silver electrode and a double junction type saturated Ag/AgCff reference electrode were used to measure the EA value (the configuration of the electrode was based on the 57-197534 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 pH value of the system was kept constant at 3.0.
% nitric acid aqueous solution.

After adding Solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then divided into 5 parts, each of which was divided into 5 parts using a 5% solution of naphtholsulfonic acid acetaldehyde resin (average degree of condensation of about 5, bound sulfuric acid 30% by weight). After that, 1200ml of an aqueous solution of ossein gelatin (containing 60g of ossein gelatin) was added, and the pH was adjusted with a 3% sodium carbonate aqueous solution or a 6% nitric acid aqueous solution. After dispersing by stirring at 55°C for 30 minutes, the final emulsion was adjusted to 1500 mQ.The final emulsion was prepared by adjusting the residual amount of the tolsulfonic acid acetaldehyde resin to the amount shown in Table 2. The degree of sedimentation was adjusted by adjusting the pH.

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

The average grain size of the silver chlorobromide grains contained in the obtained emulsion was 0.
．． 85% of the total number of 20 μm particles have a particle size of 0.14 to 0.2
6μ exposure table 2 Sensitizing dye A Naphtholsulfonic acid acetaldehyde resin residual amount (per mole of silver halide) CtbCHzCN Sensitizing dye B The residual amount was measured by spectroscopic absorption method, Shimadzu spectrofluorescence machine RF-5
It was measured by 30.

The obtained emulsions (A) to (E) were each subjected to total sulfur sensitization, and sensitizing dye A was added to 301)+4-hydroxy-6 as a stabilizer per mole of silver halide contained in the emulsion. - Ig of methyl-1,3,3a,7-chitrazaindene was added, sensitizing dye B was added to the sensitizing dye B contained in the emulsion, then 800 mg of the tetrazolium compound shown in T-36 was added per mole of silver halide, and further p-dodecylbenzene was added. Sodium sulfonate 300s+g, styrene-maleic acid copolymer polymer 2g1 styrene-butyl acrylate-acrylic acid copolymer latex (average particle size approx. 0.251Z)
m) Add 15g as shown in Table 3, and
19941J+ coated onto a subbed polyethylene terephthalate film base as described in Example (1).

At that time, the amount of gelatin was 2.0 g/+s'' in the emulsion layer and 1 g/+s in the protective layer.
．． 0g/m", Ag amount 4.0g/a" Tona 6, j:
Ur: Processing: 10-g/m'' of bis-(2-ethylhexyl)sulfosuccinate as a spreading agent, 15 mg/s'' of Polmarin as a hardening agent, and 8 layers of glyoxal were simultaneously coated in multiple layers.

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 large concentration changes due to pressurization are ranked 11, those with no concentration changes are ranked 10, and 10
A graded evaluation was performed.

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

Development processing conditions> (Process) (Temperature) (Time) (Tank capacity)
Image 34℃ 15 seconds 20Q constant
Arrival 34℃ 15 seconds 20Q water
Wash 18℃ 10 seconds 1512 dry
Drying at 40° C. for 10 seconds Each step also includes so-called wading conveyance time until the next step.

Dry to Dry time is 50 seconds.

The results are shown in Table 3.

Developer formulation> (Composition A) Pure water (ion-exchanged water) 150 mQ ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50 g Potassium sulfite (55% w/v aqueous solution) 100 Q Potassium carbonate
50g hydroquinone
15g 5-methylbenzotriazole
200agl-7enyl-5-mercaptotetrazole Drag Potassium hydroxide Maximum potassium to adjust the pH of the working solution to 1014 4.5g (composition) Pure water (ion-exchanged water) 3i+Q diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 5mg Acetic acid ( 90% aqueous solution) 0.3 Otori a 5-nitroindazole 110mg1-
7 x Nyl-3-pyrazolidore 700mg
Butylamine diethanolamine 15g When using a developer, it was dissolved in 500I of water in the order of the above composition A1 and finished to 112 before use.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0 heavy a Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g Sodium citrate dihydrate
2g acetic acid (90% w/w aqueous solution)
13.6mff (composition) Pure water (ion exchange water) 17tm (1 sulfur # (50% w/w aqueous solution) 4.7g
When using an aluminum sulfate (aqueous solution with an AQiOs equivalent content of 8.1% v/w) fixing solution, it was dissolved in 500 m+12 of water in the order of the above composition A1 and finished to 112. The pH of this fixer was about 4.3.

From the results in Table 3, it can be seen that the samples of the present invention have superior pressure resistance compared to the comparison.

Example 2 A similar experiment was conducted in Example I 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 g per mole of silver halide. ~8.0g, and a hydrophilic colloid layer on the side containing the emulsion layer with respect to the support contains 0.2 to 3.0g/m^2 of a latex polymer. material. (2) A method for processing a silver halide photographic material, which comprises processing the silver halide photographic material according to claim 1 within a developing 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.