JPH02150836A - Image processing method - Google Patents

Abstract

PURPOSE:To decrease unequal development in spite of a short-time processing and to improve after-colors by condensing and settling silver halide particles by modified gelatin and removing the dissolved matter. CONSTITUTION:An automatic developing machine having >=1,500mm/min line speed is used, by which the photosensitive silver halide photographic sensitive material is subjected to the development processing. The photosensitive silver halide emulsion of the photosensitive material is obtd. by condensing and settling the silver halide particles formed by adding a water soluble silver salt and water soluble halide into a soln. contg. protective colloid by modified gelatin and removing the dissolved matter. The hard contrast, the good after colors and the decreased unequal development are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image processing method for developing a silver halide photographic light-sensitive material using an automatic processor.

(Background of the Invention) In recent years, the consumption of silver halide photosensitive material T4 has been steadily increasing.As a result, the number of processed silver halide photosensitive materials (1" L photosensitive material) has increased. There is a demand for speeding up the development process, that is, increasing the throughput within the same amount of time.

The above trend can also be seen in the printing plate making field.

In other words, as the immediacy of information and the increase in the number of times information is being processed are increasing, it is becoming necessary to shorten the turnaround time for printing and plate-making work, and also to handle larger quantities. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly.

One way to shorten the development processing time is to shorten the length of the processing line. However, when developing with a roller conveyance type automatic developing machine, if you try to shorten the length of the processing line to shorten the development processing time, a) a decrease in density;
Problems such as b) deterioration in tmm quality, C) occurrence of uneven development, and d) occurrence of uneven fixing occur. These problems are 20
When processed in less than seconds, the density of the characteristic curve is from 0.3 to 1
．． This phenomenon is particularly likely to occur in halogenated photosensitive materials whose gamma defined by 5 is 4 or more.

An effective way to solve these problems is to reduce the amount of gelatin in silver halide photographic materials.
If the amount of gelatin is reduced, the graininess of the photographic image is likely to deteriorate, and the low-coolness portions tend to drag.

Another method is to improve the agitation in the processing tank, but since the processing tank is made smaller depending on the length of the processing line, improving the agitation will cause waves on the processing liquid surface, which will cause problems. A problem arises that causes unevenness to deteriorate.

(Disclosure of the Invention) An object of the present invention is to provide an image processing method that causes less loss of density, less uneven development, and good residual color even though it is a short processing time.

The object of the present invention is to achieve a line speed of 150011s.
An image processing method in which a light-sensitive silver halide photographic light-sensitive material is developed using an automatic developing machine of /win or higher, the light-sensitive silver halide emulsion in the photosensitive halide daughter photographic light-sensitive material comprising: Silver halide grains produced by adding a water-soluble root salt and a water-soluble halide to a solution containing a protective colloid are precipitated by ijJ1m with modified gelatin to remove dissolved substances. This is achieved by image processing methods.

In particular, the line speed of an automatic processor is 1800mm/
min or more, more preferably 2000 mm/min
It is desirable that the development processing time be within 15 seconds.

Furthermore, the above-mentioned problems tend to occur when processing silver halide photographic materials whose characteristic curve has a density defined by T of 0.3 to 1°5, which is 4 or more (particularly 6 or more). The present invention is particularly effective in processing such silver halide photographic materials.

The modified gelatin used in the present invention is preferably a gelatin in which at least 50% of the amino groups of the gelatin molecule are HA'd with 6 groups of acyl, carbamoyl, sulfonyl, thiocarbamoyl, alkyl and/or aryl.

Examples of "111fi" groups for amino groups in gelatin are U.S. Pat. No. 2,691,582, U.S. Pat.
It is described in No. 25153.

Useful substituents include (1) acyl groups such as alkylacyl, arylacyl, acetyl, and directly substituted and unsubstituted benzoyl; (2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl; (3) alkylsulfonyl and aryl. Sulfonyl groups such as sulfonyl, (4) thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl, (5) straight chain and branched alkyl groups having 1 to 18 carbon atoms, (6)
) Substituted and unsubstituted aryl groups such as phenyl, naphthyl, pyridyl, aromatic heterocycles such as furyl, and the like.

Among them, preferred modified gelatin has an acyl group (-COR
') or a carbamoyl group (-CON(R'')R').

In addition, pl is a substituted, sterile IIA aliphatic group (e.g., an alkyl group having 1 to 18 carbon atoms, an allyl group), an aryl group, or an aralkyl group (e.g., a phenethyl group), and R8 is a hydrogen atom, an aliphatic group, It is an aryl group or an aralkyl group.

Particularly preferred is the case where R" is an aryl group and "is a hydrogen atom.

Specific examples that can be used as modified gelatin in the present invention are illustrated below using amino 11J1 substituents, but the present invention is not limited thereto.

Exemplary modified gelatin (amine group substituent) COC4119(t) COC
1h (, -7 G-8 The use of this modified gelatin agent used in the desalting treatment is not particularly limited, but it is 5 to 70%, preferably 10 to 50%, of the total amount of piratin in the emulsion layer. It is desirable that

The silver halide emulsion used in the photosensitive material 4 of the present invention includes conventional silver halide emulsions such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc. The halogenated root particles may be obtained by any of the acid method, neutral method, and ammonia method.

The halide root grains may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide tJI composition differs between the inside and surface layer of the grain, and the latent image is mainly It may be a particle that is formed on the surface or a particle that is formed inside the particle.

Any shape of the halogenated root particles according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225
, No. 666, JP-A-55-26589, JP-A-55-
Specifications such as No. 42737, The Journal of Photographic Science (J, PhoLgr, 5
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared by the method described in literature such as Cl., 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The halogenated root particles according to the present invention may have a single shape, or may be a mixture of particles of various shapes.

Although any grain size distribution may be used, monodisperse emulsions are preferred in the present invention. As for the perfect halogenated grains in the monodispersed emulsion, the halogenated grains contained within a grain size range of 120% around the average grain size r account for 60% or more of the total silver halide grain weight. is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Particularly preferred highly monodispersed emulsions of the present invention have a degree of monodispersity defined by 20 or less, more preferably 15 or less.

It is desirable that the average particle size of the halogenated root particles is 0.4 μ or less, preferably 0.3 μ or less.

Photosensitive silver halide emulsions are made without chemical sensitization.
Although so-called pri@1Live emulsions can be used as they are, they are usually chemically sensitized.

For chemical sensitization, Glnfkides or Zelil
Van et al.'s book, or I-1, Pr1eserjl
Die Grundlagen der Photo
graphischen Prozesse wit
Silberhalogeniden, Aka
dcmische VcrlaBsecsellsc
hafL, 1968 can be used.

That is, sulfur sensitization using a sulfur-containing compound capable of reacting with ions or active gelatin, reduction sensitization using a reducing substance, noble metal compounds using gold or other noble metal compounds, etc. may be used alone or in combination. Can be done. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. Specific examples thereof include U.S. Patent No. 1,574,944.
No. 2,410,689, No. 2,278.94
No. 7, No. 2.728.668, No. 3165619
It is described in No. 5J. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic 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
．． No. 983.609, No. 2,983.610, and No. 2.694.631. For noble metal sensitization, in addition to kumquat salts, complex salts of metals in group II of the same table, such as platinum, iridium, and palladium, can be used; specific examples thereof are as described in U.S. Pat. 2,4
48.060, British Patent No. 618.061, etc.

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 16g value is 5 to 11, especially 7 to 9. It is preferable to maintain the temperature at 40 to 90°C, particularly preferably 45 to 75°C.

In practicing the present invention, for example, 4-hydroxy-6-methyl 1.3.3
Various stabilizers can also be used, including a, 7-titrazaindene, 5-mercapto-1 phenyltetrazole, and -mercaptobenzothiazole.

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 may be formed by cadmium salt, zinc salt, complex salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, iron salt or Metal ions can be added using salts to be contained inside the particles and/or on the surface of the particles.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, or infrared light using a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemin cyanine dyes, styryl dyes, and hemio;tosonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to 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, o-tosazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, such as pyridine nucleus, and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, such as indolenine nucleus, benzindolenine nucleus, indole nucleus, and benzoxazole nucleus. , naph[oxazole nucleus, benzodeazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be filA on carbon atoms.

Merocyanine dyes or complex melonanine dyes include nuclei having a ketomethylene structure such as birapurin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,
5- to 6-membered nuclei such as 4-dione nucleus, thiazolidine-2,4 dione nucleus, rhodanine nucleus, and thiopalpituric acid nucleus! I
! Ring nuclei 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. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion. Halogenated SR1
About 1.0XIO-' to about 5X10 of exacerbating pigment per mole
-' moles are preferred, particularly at concentrations of about 4.times.10-' to 2.times.10-' moles of sensitizing dye per mole of silver halide.

More specific examples of aggravating dyes that can be 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 Patent No. 2,231.658, US Patent No. 2,493.148, and US Patent No. 2,503.776. No. 2,519.001,
No. 2,912,329, No. 3,656.9513,
Same 3. (No. i72.897, No. 3.694217,
No. 4,025,349, No. 4,046,572, British Patent No. 1,242.588, Japanese Patent Publication No. 4.1-1403
No. 0, No. 52-2.1844, JP-A-48-7313
No. 7, No. 6LI72140, etc., and examples of sensitizing dyes used in green-sensitive silver halide emulsions include those described in U.S. Patent No. 1,939.2.
January, 2,072,908 August, 2,739.14
No. 9, No. 2,945.763, British Patent No. 505°97
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent Publication No. 48-42172.
Enhancement dyes used in red-sensitive and infrared-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 2,270,378, No. 2,442710,
As described in JP-A No. 2,454.629, JP-A No. 2,176.280, JP-A-49-17725, JP-A-50-62425, JP-A-61-2983f3, JP-A-60-80841, etc. Cyanine dye, me [1 cyanine dye or? A representative example of such dyes is M cyanine dye.

These aggravating dyes may be used alone or in combination. Combinations of enhancing dyes are often used, especially for the purpose of supersensitization. A typical example is U.S. Patent No. 2.
No. 688.545, No. 2,977.229, No. 3,3
No. 97.060, No. 3,522,052, No. 3,52
No. 7.641, No. 3,617.293, No. 3,628
, No. 964, No. 3,666゜480, No. 3,672.
No. 898, No. 3,679.428, No. 3703.37
No. 7, No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026.707, British Patent No. 1, No. 344.281, No. 1.50”1.8
No. 03, Special Publication No. 43-4936, No. 53-12375
No., JP-A-52-110618, JP-A No. 52-1099
It is described in No. 25, etc.

Further, in the silver halide photographic material i1 of the present invention, in order to obtain a high-contrast image, it is desirable that a hydrazine compound or a tetrazolium compound be added.

For example, hydrazine derivatives (e.g. U.S. Pat. No. 4,166)
．． No. 742, 1.16El, 977, 4,22
No. 1.857, No. 4,224.401, No. 4,243
．． No. 739, No. 4,272.606, No. 4,311.
As seen in No. 781, a negative silver halide photographic light-sensitive material to which a specific acylhydrazine compound) has been added,
A high-contrast negative image can be obtained by processing with a solution containing R1111, 0 to 12.3 and a sulfite preservative of 0.15 mol/1 or more.

Examples of hydrazine derivatives include US Pat. No. 4,478.
In addition to the aryl hydrazides in which a sulfinic acid residue is bonded to the hydrazo moiety described in No. 928, the following -
Examples include compounds represented by the formula m.

General formula (1) % formula % In the formula, R1 represents an aliphatic group or an aromatic group, R2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group Device 1 Negative or unsubstituted It represents an alkoxy group or a substituted or unsubstituted aryloxy group, and G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an Nvl-substituted or unsubstituted iminomethylene group.

-a formula (for the hydrazine derivative shown in JP-A No. 6
Although it is disclosed in No. 2-210458, the specific example compounds described in the same publication can also be used in the present invention.

The hydrazine compound is added to the silver halide emulsion layer and/or the non-photosensitive layer (hydrophilic colloid layer) on the silver halide emulsion layer side of the support, but preferably to the silver halide emulsion layer and/or the non-photosensitive layer (hydrophilic colloid layer). or its lower layer.

The amount added is 101 to 5×10-”mol/fil.
1 mol is preferred, more preferably 10-S to 2X10
-”Mole/1 mole of resentment.

Preferred tetrazolium compounds include those represented by the following general formula (If), (Ill) or (rV).

(Space below) General formula (II) General formula (1) General formula ([V) In the formula, R+, Rs, R41Rs, Rs, Rs, R+
. and R.

are alkyl groups (e.g. methyl group, ethyl group,
propyl group, dodecyl group, etc.), alkenyl group (e.g. vinyl group, allyl group, propenyl group, etc.), aryl group (e.g. phenyl group, triJLM, hydroxyphenyl group,
carboxyphenyl group, aminophenyl group, mercaptophenyl group, α-naphthyl group, β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.), and heterocyclic groups (such as 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, R, and R1 each represent an allyl group, a phenyl group which may have a substituent, a naphthyl group which may have a substituent W, a heterocyclic group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group) group, butyl group, mercaptomethyl group, methylcaptoethyl group, etc.), hydroton group, carboxyl group or its salt, alkoxycarbonyl group (e.g. methoxycarbonyl group, ethquincarbonyl group, etc.), amino group (
D represents a divalent aromatic group, and E represents an alkylene group, an arylene group, an aralkylene group. represents a group selected from
X- represents an anion, and n represents an integer of 1 or 2. However, when the compound forms an inner salt, n is l.

Incidentally, specific examples of the tetrazolium compound represented by the above general formula are described in JP-A-62-111253, and these compounds can also be used in the present invention.

One preferred embodiment 841 of the present invention is to add the tetrazolium compound according to the present invention into the silver halide emulsion layer. In another preferred embodiment 811 of the present invention, it is added to the non-photosensitive aqueous colloid layer directly adjacent to the silver halide emulsion layer or to the non-photosensitive hydrophilic colloid layer adjacent via an intermediate layer. Ru.

In another embodiment, the tetrazolium compound according to the present invention is dissolved in a suitable conventional solvent, such as alcohols such as methanol and ethanol, ethers, esters, etc., and the photosensitive material is halogenated by an overcoating method or the like. It may be directly applied to the outermost layer on the side of the silver emulsion layer and incorporated into the photosensitive rice grains.

Further, the tetrazolium compound according to the present invention has an amount of 1X10 per mole of silver halide contained in the photosensitive material t4 of the present invention.
It is preferable to use the J·n range from -'' mol to 10 mol, especially from 2X10-' mol to 2XIO-' mol.
stomach.

Gelatin is usually used as a binder or protective colloid for the silver halide emulsion used in the present invention, but in addition to gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, Hydroxyethyl cellulose, carbonide dimethyl cellulose 4 Nose JIi Sugar derivatives such as loose derivatives, agar, sodium alginate, starch derivatives, polyvinyl alcohol, polyN vinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl pyrazole, etc. Alternatively, various synthetic hydrophilic polymeric materials such as copolymerized materials can be used.

Further, it is desirable that the weight of gelatin on the photosensitive layer side of the photosensitive silver halide photographic material jl in the present invention is 3.5 g/+n'' or less, preferably 3 g/m'' or less.

The silver halide photographic feed according to the present invention may contain a water-soluble dye 4 in the hydrophilic colloid layer as a filter dye 4 or for the purpose of preventing irradiation, preventing halation, and other purposes. For this kind of dyed tea,
Included are oxonol dyes, hemioxonol dyes (4), styryl dyes, merocyanine dyes (T4), cyanine dyes and azo dyes (1). Among them, oxonol dye, Hemio:
Tosonol dyes and merocyanine dyes are useful.

In the silver halide photographic polishing layer 4 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 shade.

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 t4. That is, many compounds known as stabilizers can be added, such as azoles, heterocyclic mercapto compounds, thioketo compounds, azainthenes, benzenethiosulfonic acids, benzenesulfinic acids, and the like.

An example of a compound that can be used is by K. Mees, The
Theory of Photographic Pr
occess, 3rd edition, 1966, citing the original literature.

For more detailed examples of these and how to use them, see, for example, U.S. Patent Nos. 3.954.474 and 3.98
Reference may be made to the descriptions in each specification of No. 2.947 and No. 4,021,248, or Japanese Patent Publication No. 52-28660.

Moreover, the silver halide photographic photoluminescent material of the present invention is photo+? !
During stratification, U.S. Patent Nos. 3,411.911 and 3,4
11.912, Japanese Patent Publication No. 45-5331, and the like.

The silver halide photographic material of the present invention may contain the following various additives, such as thickeners or plasticizers, such as those described in U.S. Pat.
Publication No. 39, West German Application Publication No. 1, 904, 604
specification, JP-A No. 48-63715, JP-A No. 45-1
Publication No. 5462, Belgian Patent No. 762.833,
U.S. Patent No. 3,767°410, Belgian Patent No. 5
Substances described in each specification of No. 58.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc., various hardening agents such as aldehyde type, and ultraviolet absorbers, such as U.S. Patent No. 3,253, No. 921,
There are compounds described in various specifications of British Patent No. 1,309,349.

Furthermore, as coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548,532, 1.21 (i, No. 389,
U.S. Patent No. 2,026,202, U.S. Patent No. 3,514゜2
Each Meita book of No. 93, Special Publication No. 44-26580, No. 4
No. 3-17922, No. 43-17926, No. 43-3
166, 48-20785, French Patent No. 202.588, Belgian Patent No. 773,459, Mei III, Japanese Patent Application Laid-Open No. 48401118, etc. Among these, anionic surfactants having a sulfonic group, such as succinic acid ester sulfonates, alkylbenzene sulfonates, and alkylbenzene sulfonates, are particularly preferred.

In addition, as an antistatic agent, Japanese Patent Publication No. 4G-24159, Japanese Patent Application Laid-open No. 48-89979, and U.S. Pat.
Specifications of No. 2.157 and No. 2.972.535,
JP 48-20785, 4B-43130, 48-90391, JP 46-24159, 4
No. 6-39312, No. 48-43809, Japanese Unexamined Patent Publication No. 1973
There are compounds described in each publication of No. 33627.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.3 to 7.
．． In the case of multilayer coating, it is preferably in the range of 5.
It is preferable that the pl+ of the coating liquid obtained by mixing the coating liquids of each layer in the ratio of coating amounts is in the above range of 5.3 to 7.5.

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 Patent No. 1,296.995, and British Patent No. 1 Inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc as described in US Pat. No. 2.322.037, Belgian Patent No. 625.451 Alternatively, the lees derivatives described in British Patent No. 981.198, the polyvinyl alcohol described in Japanese Patent Publication No. 44-3(i, 13), and the polystyrene described in Swiss Patent No. 330.158. or polymethyl methacrylate, polyacrylonitrile described in U.S. Pat. No. 3,079,257, U.S. Pat. No. 3,02
Organic particles such as polycarbonate described in 2.169 can be included.

In the light-sensitive material of the present invention, the constituent layers include slipping agents, such as U.S. Pat.
Higher aliphatic higher alcohol esters described in the specification of No. 0, casein described in the specification of U.S. Patent No. 3,295,979, higher fatty acid calcium salts described in the specification of British Patent No. 1,263.722, British patent cylinder 1.313,3
No. 84, U.S. Patent No. 3,042,522, U.S. Patent No. 3,48
Dispersions of liquid paraffin, which may contain silicon compounds described in each specification of No. 9,567, can also be used for this purpose.

The photosensitive material of the present invention may further contain additives of type h depending on the purpose.

These additives are described in more detail in Research Disclosure Volume 176 I Lem17G43 (1975, January 1975).
February) and Volume 187 I Le Dance 18716 (1979
(November 2013).

In carrying out the silver halide photographic material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene tereclate, polycarbonate, baryta layers or α- Examples include paper coated or laminated with an olefin polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), or the like. The support may be colored using dyes or pigments,
The surface of these supports, which may be painted black for the purpose of blocking light, is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating treatment is preferably the treatment described in JP-A-52-10-1913, JP-A-59-18949, JP-A-59-19940, and JP-A-59-19941.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on the 1th layer by a seed coating method. For application,
A dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

Next, the development, fixing, washing, and drying steps in the present invention in which the development time is within 20 seconds, preferably within 15 seconds will be described.

The developing agent used in the black and white developer used in the present invention has a dihydroxybenzene chain and 1-
A combination of phenyl-3-pyrazolidones is most preferred, but of course a p-aminophenol developing agent may also be included.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, 2.5-
Examples include dichlorohydroquinone, 2.3-dibromohydroquinone, and 2.5-dimethylhydroquinone, with hydroquinone being particularly preferred.

The developing agents for ■-phenyl-3-pyrazolidone or its derivatives used in the present invention include 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1 -phenyl-4,4-dihydroxymethyl-3-virapritone and the like.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminephenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is usually 0. It is preferable to use O1 mol/P to 1.2 mol/l.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite,
Examples include formaldehyde heavy sodium 68 M + thorium. The amount of sulfite is preferably 0.2 mol/l or more, particularly 0.4 mol/l or more, and the upper limit is preferably 2.5 mol/l.

The pH of the developer used in the present invention is preferably in the range of 9 to 13, more preferably in the range of pHio to 12.

Alkaline agents used to set pl+ include pl+ regulators such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-61-28708 (borates), JP-A-60-
No. 93439 (e.g. sucrose, acetoxime,
Buffers such as 5-sulfosalcylic acid), phosphates, and carbonates may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Adhesive agents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may also contain an antifoggant such as a mercapto compound, an indazole compound such as 5-nitroindazole, or a pentztriazole compound such as 5-methylbenztriazole (and, if necessary, a coloring agent, a surfactant, or a degreaser). Foaming agent, water softener, JP-A-56-1
It may also contain the amino compounds described in No. 06244.

In the present invention, a liquid stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

In the developer of the present invention, amine compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, P.A. Meson, “Photographic Brothecine Gemistry”, published by Focal Press (1
966), pp. 226-229, 2. summer 93
．． No. 015, No. 2,592,364, Japanese Unexamined Patent Publication No. 1973-6
Those described in No. 4933 may also be used.

In the present invention, the development processing time refers to the time from when the photosensitive material to be processed is immersed in the developing tank liquid of an automatic processor until it is immersed in the next fixing solution. This refers to the time from immersion to the next washing tank solution (stabilizing solution).

In addition, the washing treatment time refers to the time spent immersed in the washing tank liquid, and the drying treatment time refers to the drying process in which hot air is blown at a temperature of usually 35°C to 100°C, preferably 40°C to 80°C. This refers to the time that the drying zone, which is installed on the automatic processor, is in the drying zone.

The development processing temperature and time are about 25°C to about 50°C for 15 seconds or less, preferably 6 seconds to 30°C to 40°C.
It is 15 seconds.

The fixing solution is an aqueous solution containing thiosulfate, and has a pll of 3°8.
Above, preferably 4.2 to 5.5.

Fixing agents include sodium periosulfate and ammonium thiosulfate, but they contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of fixing agent used may be changed as appropriate. -a is about 0.1 to about 6 mol/2.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride,
Examples include ammonium sulfate and potassium alum.

In the fixing solution, tartaric acid, citric acid, or their derivatives may be used singly or in combination of two or more. It is effective to use these compounds in an amount of 0.005 mol or more per 1N of fixer, especially 0.01 mol/l to 0.03 mol/l.
l is particularly effective.

Specifically, the fixing solution may contain a preservative (sulfite), etc., as desired. , bisulfites) 1.111 slowing agents (acetic acid, nitric acid), pH adjusting agents (e.g. sulfuric acid), chelating agents capable of water softening, and compounds described in Japanese Patent Application No. 6O-2135 (I2). .

Fixing temperature and time are approximately 20°C to approximately 50°C for 6 seconds to 1
minutes is preferred, but 6 seconds to 30 seconds at 30°C to 40°C is more preferred, and still more preferably 6 seconds to 30°C to 40°C.
seconds to 15 seconds.

If the fixer concentrate is replenished with diluting water into the automatic processor in the method of the present invention as the light-sensitive material is processed,
As in the case of the developer, it is most preferable that the fixer concentrate is composed of an L agent.

It is pll that the fixer and developer can exist stably as l agents.
It is 4.5 or more, more preferably 1114.65 or more. The upper limit of pll is not so strict, but if the pH is too high
If it is fixed with water, the membrane p becomes high even after washing with water, and the membrane swelling becomes large, so that the dry St1. Since the load becomes thick, the limit is up to p117. In a fixing solution that hardens a film using an aluminum salt, the limit of ρ11 for preventing precipitation of the aluminum salt is 5.5.

In the present invention, either the developing solution or the fixing solution does not require dilution water as described above (i.e., it is replenished as an undiluted solution).
It may be a so-called working liquid.

The mixing ratio of each concentrate with the supply liquid and dilution water to the processing tank liquid can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8. The total amount of each of these developing solutions and fixing solutions is from 50ml to 1500+/! for 1IIIffi of the photosensitive material. It is preferable that

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mildew water for washing or as a stabilizing solution, 3I per 1Illz of photosensitive material can be reduced! Not only is it possible to conserve water for replenishing the following, but the piping of the machine equipment is no longer required, and the number of stonks can be reduced.

When washing with a small amount of water, a patent application from 1983 to 1729
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with water treated with anti-mold means, according to the treatment, is
As described in Japanese Patent No. 35113, the pretreatment process of fixing f1 can also be used as a processing solution.

As anti-mildew means, the ultraviolet irradiation method described in JP-A No. 6O-2 (i3939), the method using a magnetic field described in JP-A No. 60-263940, and the ion conversion resin described in JP-A No. 61-131632 are used. A method using a fungicide described in Japanese Patent Application No. 60-253807, No. 60-295894, No. 61-63030, No. 61-5139 (I) can be used.

Furthermore, L, [i, West “Water Qual
ity Cr1teria'Photo Sci &
[! ng, Vol, 'J No, 6 (
19 (i5), M], Beach “Microbio
Logical Growth in Motio
n-PicLure Processing” SMM
E Journal Vol, 85. (1976)
,R.

0, Deegan, “Photo Proce
ssing 1lash Water Bioclde
s” J, Imaging Tech, Vol 10
．． Na6 (1984) and JP-A-57-8542,
No. 57-58143, No. 5B-105145, No. 5
No. 7-132146, No. 5B-18f331, No. 57
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in Japanese Patent Nos. 97530 and 57457244 can also be used in combination.

In addition, the washing bath includes R.T. Kreisan, J., In.
+age, Tech 10. (6) 242 (1984)
The isothiazoline compound described in RES[! to R
CII 口15CLO3UR [i Volume 205, l ten
Isothiazoline compounds described in 20526 (May 1981 issue), Volume 228, Item 2284
5 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as antibacterial agents (Mlcroblocide).

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-Phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde 1', Riji 1 Rua t! 1-amide, p-hyroxyammonium 7a, fragrant ester, 2-(4,thiazoline)-benzimidazole, benzisodeazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N-(fluorodichloro Methylthio)-phthalimide, 2,4.4
'-) Lichloro-2' hydroxydiphenyl ether, etc.

It is preferable that the water treated with anti-mildew measures and stored in a water stock tank be used both as dilution water for the undiluted solution of processing solutions such as the developer and fixer, and as washing water, since it takes up less space. Dilution water treated with anti-mold and washing water (or stabilizing liquid) can be stored separately in separate tanks, or only one of them can be taken directly from the tap.

When stored in separate tanks, the washing water (or stabilizing bath) can contain various additives in addition to applying anti-mildew measures as in the present invention.

For example, a chelate compound having a log value of chelate stability with aluminum of 10 or more may be included. These are effective in preventing scuttling in washing water when the fixer contains an aluminum compound as a hardening agent.

Specific examples of chelating agents include ethylenediaminetetraacetic acid (logK 16.1, same below), cyclohexanediaminetetraacetic acid (17,6), diaminopropanoltetraacetic acid (13,8), diethylenetriaminepentaacetic acid (18
,4), I-lyethylenetetraminehexaacetic acid (19,7
), and their sodium salts, potassium salts, and ammonium salts, and the amount added is preferably 0. O1~lO
g/4, more preferably 0.1-5c/j! It is.

Furthermore, in addition to the image stabilizing agent, various surfactants can be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of cationic type, negative ion type, nonionic type, and amphoteric type may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane 911 (e.g. pH
3 to 8) various loose iji agents (e.g. borate, mekborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, Typical examples include aldehydes such as polycarboxylic acids (used in combination with polycarboxylic acids, etc.) and pomarin. In addition, chelating agents, fungicides (thiazole type, isothia'l/'-al type, halogenated phenol,
Various additives such as sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardening agents may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, it is possible to remove coloring agents such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. from the processing solution. I! It is preferable to add an ammonium salt in order to improve image storage stability.

The water washing or stabilization bath temperature and time using the above method is 0゛C.
~50°C for 6 seconds to 1 minute is preferred, but 15″C to 40°C
6 seconds to 30 seconds at °C, more preferably 15 °C
6 to 15 seconds at ~40°C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is carried out at about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 1 minute, more preferably at 40°C.
C to 80"C for about 5 seconds to 30 seconds.

In addition, so-called D until development, fixing, washing and drying.
The total processing time for ry to dry is within 100 seconds, preferably within 60 seconds, and even within 50 seconds.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of emulsion) Solution A Water 9
．． 72 Sodium chloride gelatin I
．． 842 Silver nitrate 1700
g In the above solution Δ kept at 38°C, pH 3.5
, while maintaining the pAg at 7.8, the above solution B and solution C were simultaneously added functionally over 60 minutes, and after continued stirring for an additional 10 minutes, the pH was adjusted to 5.8 with an aqueous sodium carbonate solution, and one of the two portions was added. Modified gelatin (pre-H2G-1) 019% aqueous solution 1400c shown in Table 1 was added to the emulsion.
c28m! 0II11 05g 3.8p 95,.

The pH of the emulsion was adjusted to 4.5 with 56% acetic acid at 35°C.
flocculate and decant as
Remove excess aqueous salts by washing with water. Then add 1.91 of water to make up to 11 minutes and add 4% Na0II.
After setting the pll to 5.3 and stirring for 5 minutes, add 56% acetic acid again to 1.
11 was adjusted to 4°5, and the excess salt in the aqueous solution was removed in the same manner. To it, add 1.91 water and 4% Na01
1 to pH 5.7, and then dispersed at 55°C for 30 minutes.

In addition, the other emulsion contains 20% magnesium sulfate aqueous solution 11
and 5% aqueous solution of polynaphthalene sulfonic acid 1.26N
The emulsion was flocculated at 35°C, decanted, and washed with water to remove excess salts from the aqueous solution. Then, add 1.9e of water to it and disperse it,
20% magnesilanosulfate, aqueous solution 0.451 is added again, and excess water-soluble salts are removed in the same way. And 1.
Add 9℃ water and 70.5g gelatin and boil at 55℃ for 3 minutes.
Tlk for 0 minutes.

As a result, two types of grains having 35 mol % of silver bromide, 65 mol % of silver chloride, an average grain size of 0.24 μm, and a distribution width of 9 are obtained.

Then add 12ml of citric acid (1% water) to these.
, 5% sodium chloride water) 8 liquid was added and p
To the emulsion adjusted to H5.5 and PAg 7, 120 ml of a 0.1% sodium periosulfate aqueous solution and 80 ml of a 0.2% chloroauric acid aqueous solution were added, and the mixture was aged at 60°C to reach the highest sensitivity. did.

The above emulsion was divided into 11 portions, each containing 0.5 ml of l-phenyl-5-mercaptotetrazole as an antifoggant.
% solution to 2511, 4-hydroxy-6 as stabilizer,
Methyl-1,3,3a, ? -Tetrazaindene 1
% solution 180mf, 10% aqueous gelatin solution 400mf
After curing the ripening process, add infrared sensitizing dyes (a) and (
Add 15+1 of each 0.1% methanol solution of b), and further add 5Qml of 10% solution of hydroquinone as an anti-capri agent and 50ml of 5% solution of potassium bromide.
Add 19ml of 20% saponin aqueous solution as a spreading agent.
1. 50ml of a 4% aqueous solution of styrene-maleic acid polymer as a thickener, 30g of polymeric polymer Latinx of ethyl acrylate, l-hydroxy as a hardening agent, 3
, 5-dichlorotriazine sodium salt and formalin were added, and the above emulsion was coated on a subbed polyethylene terephthalate support at a density of 3.5 g/m! , gelatin 2.0
c/m", and as a protective film, add 100ml of a 10% potassium bromide aqueous solution to an aqueous solution of 500g of gelatin.
j! 1-decyl-2-(3
-Isopentyl)succinate-2-sulfonic acid sodium 1% aqueous solution 1 400nF! Added, average particle size 3.5μ
Amorphous silica was added and dispersed, and the emulsion layer and the third layer were simultaneously coated with gelatin at a concentration of 1.0 g/m''.

<Developer prescription> Pure water (ion exchange water) Approx. potassium sulfite Ethylenediaminetetraacetic acid disodium salt potassium hydroxide 5-methylbenzotriazole diethylene glycol 1-phenyl-4,4-dimethyl-3 Pyrazolidone 1-phenyl-5- Mercaptotetrazole potassium bromide hydroquinone potassium carbonate Add pure water (ion exchange liquid water) Finish to 1,000ml.

Fixer formulation> Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 800 m 1 60 g 10.5 g 300 m (1 5 g 3001I1 g 0 mg 3.5 g 0 g 5 g 24 On/! Sodium sulfite 25 g Acetic acid - Notorium trihydrate 6.5g boric acid
6g sodium citrate dihydrate 2g acetic acid (90% W/W aqueous solution)
12.5m e (composition) Pure water [ion exchange water] 17III! .

Sulfuric acid (509<w, 'w aqueous solution) 4.0
g Aluminum sulfate (Al t (h IArI content 8.1% W/W)
Water 1ati) 26.5! ! When using the fixer, the above composition A and composition 3 were washed in 500 ml of water in that order and finished to 1p.

The pl+ of this fixer was about 4.6.

The sample sample 1 thus obtained was subjected to image exposure using a semiconductor laser scanner having a wavelength of 780 na, and was processed using an automatic processor using a developer and a fixer having the above composition under the conditions shown in Table 1. D-0°15~1.5 T
The value and residual color were evaluated. Also, the concentration is 1.0 to 1.3
The film was exposed to light and processed in the same manner, and the development unevenness was evaluated. Note that the sharpness and development unevenness were divided into 10 levels and rated at 3 and 7 values. 10 is best, 1-4 is unusable,
5 or higher is a usable level.

(Hereinafter referred to as margins) From Table 1, it can be seen that the products of the present invention have high contrast and good residual color and development unevenness.

Example 2 In Example 1, replace the sodium chloride in solutions △ and B with potassium bromide and potassium iodide, add an appropriate amount of ammonia to solution C, and add pl+ while maintaining ρag at 8°5. 10 to 8, the salt was removed in the same manner as in Example I, and two types of iodobromide 5ri (silver iodide 0.5 mol%) grains with an average grain size of 0.29μ were prepared. The width of the obtained 0 distributions was 12 in both cases.

Each of these emulsions was sensitized with gold and sulfur, and prepared in the same manner as in Example 1 to prepare samples '1'. However, the dye (c) was added.

(c) I'c-Ne laser (wavelength 6
Image exposure was performed using a 32.8r++++) scanner, and evaluation was made in the same manner as in Example 1 using the following developer.

Composition of developer (Developer Iff) Hydroquinone 34 gl-Phenyl-4,4-dimethyl-3 Pyrazolidone 0.23 g Ethylenediaminetetraacetic acid 2. Sodium salt g 3-diethylamino-1,2-propanediol
1585-Methylbenzotriazole 0.4εNazSOs
76 gNaBr
3 g Nacl
1.3 g1 mol/r phosphoric acid? night night 4
Adjust the pH to 11 with condensed water to which the necessary Na0II is added to bring the pH to 11.4.

The results are shown in Table 2, and it can be seen that the products of the present invention have high contrast, good residual color, and good development unevenness. However, since it is silver iodobromide, Example 1 does not have any T value.

(Margin below)

Claims (1)

[Claims] An image processing method in which a light-sensitive silver halide photographic light-sensitive material is developed using an automatic developing machine with a line speed of 1500 mm/min or more, the light-sensitive silver halide in the light-sensitive silver halide photographic light-sensitive material The emulsion is
It is characterized by being obtained by adding a water-soluble silver salt and a water-soluble halide to a solution containing a protective colloid, condensing and precipitating silver halide particles with modified gelatin, and removing dissolved substances. image processing method.