JPH03163442A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To inhibit uneven development and to improve sensitivity by processing a silver halide photographic sensitive material with a developer having a specified compsn. within a specified development time. CONSTITUTION:A silver halide photographic sensitive material is imagewise exposed and processed with a developer of pH 9.0-12.0 contg. >=0.2mol/l sulfite in the presence of a polyalkylene oxide compd. within 15sec development time. The polyalkylene oxide compd. may be allowed to exist at any time during development and may be incorporated into the sensitive material or added to the developer. The compd. is preferably represented by formula I or II. In the formulae I, II, R<1> is alkyl, R<2> is alkylene, R is H, halogen or optionally substd. alkyl, A is an arom. ring and each of k, l, m and n is the average total number of bonding units.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide photographic materials. In particular, it relates to a method for processing silver halide photographic materials that can produce images with high sensitivity and high contrast without uneven development. (Prior Art) Various processing techniques have been used in the field of silver halide photographic light-sensitive materials, but depending on the processing method, uneven development may occur. However, there are some fields, such as the printing and plate making field, in which it is desirable to strictly suppress the occurrence of such uneven development.On the other hand, achieving high sensitivity processing is a major challenge for any photosensitive material. Furthermore, although there are fields in which high-contrast images are desired, there is still no processing method that satisfies all of the above-mentioned demands such as suppressing development unevenness, increasing sensitivity, and increasing high contrast. No proposal has been made. In particular, in recent years, there has been a demand for a reduction in processing time in various fields of photosensitive materials, but it is difficult to meet this demand and also satisfy the above requirements. [Object of the Invention] The present invention solves the above-mentioned problems and eliminates uneven development.
The purpose of this invention is to provide a method for processing silver halide photographic materials that has high sensitivity and can also achieve high contrast in images. [Means for Solving the Problems] As a result of intensive research, the present inventors have found that at least l
After image exposure, a silver halide photographic light-sensitive material having a silver halide emulsion layer is processed using a developer containing 0.2 mol/l or more of sulfite with a developer having a concentration of p}{9.0 to 12.0. The present inventors have discovered that the above objects can be achieved by a method for processing halogenated photographic materials, which is characterized by processing in the presence of an oxide compound for a developing time of 15 seconds or less, and have completed the present invention. The present invention will be explained in more detail below. A photosensitive material to be processed to which the processing method of the present invention is applied has at least one silver halide emulsion layer on a support. Therefore, one side of the support has at least an IJII silver halide emulsion layer, and the opposite side has, for example,
The support may have a packing layer consisting of a non-photosensitive layer such as a gelatin layer, or it may have at least one silver halide emulsion layer on each side of the support. In addition to the silver halide emulsion layer, the support may have non-photosensitive layers such as a protective layer, an intermediate layer, and an antihalation layer. The silver halide emulsion layer consists of 2
It is okay to have more than one layer of formality. Next, in the present invention, the photosensitive material to be processed is treated with 0.0% sulfite after imagewise exposure.
Process with a developer having a pH of 9.0 to 12,0 containing 2 mol/l or more in the presence of a polyalkylene oxide compound within a developing time of 15 seconds. Here, "in the presence of a polyalkylene oxide compound" means that the compound need only be present at least at some point in the development process, and the photosensitive material to be processed contains the compound. Alternatively, the compound may be contained in the developer. In the present invention, any polyalkylene oxide compound may be used as the polyalkylene oxide compound present during processing of the photosensitive material. Preferred ones are the following general formula (1
) or a compound represented by general formula (It). General formula (1) General formula (It) R-^-0 + CH *Cll tO -hr- H
In the above formula, R' is an alkyl group, Rz is an alkylene group, R
represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, and A represents an optionally substituted aromatic ring. Number of units k. l. m and n represent the average total number of bonding units, 50≧k
Restricted to ≧30.5≧l≧1.20≧m≧2 and 50≧n≧5. More specifically, R' has 2 to 4 carbon atoms.
It is preferable that it is an alkyl group of R! is preferably an alkylene group having 2 to 4 carbon atoms. R is preferably a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent having 6 to 20 carbon atoms in the alkyl group moiety. A is an aromatic ring which may have a substituent. Any substituent may be used for each of the above groups. The above general formula [! ], preferable alkyl groups having 2 to 4 carbon atoms represented by R' include, for example, CB. CHeClhCH1CHC}lzcH:+, and preferred alkylene groups having 2 to 4 carbon atoms represented by R2 include, for example, CFltCHt, CHzCH, ~CH
zCHzCHg-CH3. Next, typical specific examples of the compound represented by the general formula (1) (hereinafter sometimes referred to as "compound 2") that can be used in the present invention are shown. However, these are representative examples and are not limited to these. Below are example compounds in the margin! -1. 1-1. m=(va,+st)-15. n- (n+
+nm)=30I 2. 1 = l, 1- (sl +m*)-12, n-
(n+-}n*)=25! -3. 1 = 1+ s- (m+ 10 m.)-16, n
-(n,+nx)-40! -4. 1 ”3. m=(m++i+z)- s, n-
(n++nt)-15I-5.疋 = 1, m- (s, +++n) - 8, n = (nl
+nx)=201-6. 1 =1, m= (Ill +ll!) -14,
n- (nt +n!)-35I-7. 1-1. a=(m++mz)=8, n=(
n++nt)=20I-8. 1 = 5, *= (m++mt) = 10+ n-
(n++nx)=20f 9. 1 -1, *a+r(*, +*J-1(L n-(
nl+nt)-251-10. 1 −L m=(m1 +mJ − 7 + n− (
n+ +nt) -201 -11. J=4. s-(sl +mt)-10, n"(
n+ +n*) -501 -12. 1 = 4, m- (m, +mt)-10. n-
(n+ +nt) -25 These compounds were
It is possible to easily enter the precepts according to the method described in No. 6-30124. The amount of compound (1) added and the usage of the added layer are as follows. When compound (1) is contained in a light-sensitive material, the layer containing it may be any layer in the structure of the light-sensitive material, but may be a silver halide emulsion layer and/or a layer adjacent to the silver halide emulsion layer. is preferable. In order to incorporate the compound (1) into a photosensitive material, the compound (1) is dissolved in water, an organic solvent miscible with water, or a mixture thereof.
It is preferably added to a coating solution for forming a silver halide emulsion layer and/or its adjacent layer, particularly preferably in a silver halide emulsion layer. The amount of compound (1) added in the light-sensitive material is preferably 10 to 5 g, particularly preferably 100 to 2 g, per mole of silver halide. Also, the timing of adding compound (1) is determined during the production of the photosensitive material. Any time during the process can be selected, but for example, when adding it to a silver halide emulsion layer, it is preferable to add it after completing the second precept. Compound (1) is effective even when added to the developer, and in this case, it is preferable to add 50 to 10 g per liter of the developer. next,
Specific examples of the compound represented by the general formula (n) (hereinafter also referred to as "compound [l]" as appropriate) that can be used in the present invention are given below.
l) is not limited to this. Exemplary Compound I1-1 n-2 I1-3 n-4 11-5 Compound (II) may be contained in the photosensitive material or in the developer solution) When contained in the photosensitive material, compound CII ) can be added to any layer containing a hydrophilic colloid layer. The amount added varies depending on the layer to which it is added, but generally it is preferable to add it to a layer closer to the surface of the photosensitive material. When added to a silver halide emulsion layer, the amount added is usually preferably in the range of 6 to 6 g per 1!1 mole contained in the emulsion layer. The layer containing the additive, the timing of addition, and the method of addition are the same as those for compound CI). In addition, compounds (1) and (II) can be used alone,
Alternatively, either one may be used at 2N or more, or may be used in combination. If used together, their usage ratio (weight)
(1)/(II) is preferably 2/8 to 8/2, more preferably 3/7 to 7/3. Further, the total amount of sulfite used in the present invention is 50 to 0.2 mol/f in the developer for processing the photosensitive material! ．． It contains the above. Sulfites have traditionally been used in developer solutions, for example, to act as preservatives. The sulfite used in the present invention is arbitrary, and includes, for example, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite, and other alkali metal salts and ammonium salts. Other water-soluble sulfites such as salts can also be used. The amount of sulfite added is 0.2 mol/l or more, particularly preferably 0.4 mol/l or more. Also, the upper limit is 2.5 mol/I! It is generally preferable to
The pH of the developer used in the present invention is in the range of 9.0 to 12.0, more preferably in the range of 9 to 13.
More preferably, the pH is in the range of 10 to 12.

Any alkaline agent can be used to set the pH, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate! Contains A moderator. JP-A-61-28708 (borates), JP-A-609
No. 3439 (e.g., sucrose, acetoxime,
Buffers such as 5-sulfosalcylic acid), phosphates, and carbonates may also be used. The developing time in the processing method of the present invention is within 15 seconds. Preferably it is 5 to 15 seconds. In the present invention, the development time refers to the time during which the photosensitive material to be processed is substantially exposed to the action of the developer, and when using an automatic processor, the photosensitive material to be processed is immersed in the developing tank of the automatic processor. This refers to the time until immersion in the next fixer. Next, in the processing method of the present invention, the photosensitive material to be processed is preferably processed using an automatic processor with a line speed of 1000 mm/min or more. The line speed is more preferably 1500 m+/min or more, even more preferably 1800 mm/min or more.

When processing using an automatic processor, the type of automatic processor and
There are no limitations on the type, and for example, a roller conveyance type automatic developing machine can be used. Such an automatic processor is described in U.S. Pat. No. 3,025,779;
No. 545,971, etc. This type of automatic processor generally consists of parts that perform four steps: development, fixing, washing, and drying, and it is preferable that the method of the present invention is also carried out in these steps.

In the present invention, the processing time is so-called y to dry.
The time (from the moment the leading edge of the photosensitive material to be processed enters the film insertion section of the automatic processor to the moment the leading edge emerges from the automatic processor after being processed) must be 60 seconds or less. is preferred. In addition, the fixing time is less than 20 seconds,
Furthermore, it is preferable that the washing time is 15 seconds or less, and the washing time is 15 seconds or less.
It is preferable that it is 0 seconds or less.

The pH of the fixer is preferably in the range of 4.0 to 5.0. Next, the photosensitive material to be processed in the present invention will be described in more detail. The light-sensitive material only needs to have at least one silver halide emulsion layer, and there are no other restrictions on its structure. The amount of gelatin on the side having the silver halide emulsion layer of the photosensitive material to be processed is preferably 3.0 g/rrf or less, more preferably 2.6 g/nf or less. The silver halide used in the silver halide emulsion layer is any one used in ordinary silver halide emulsions, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. can be used.

Preferably, a silver halide emulsion having a silver chloride content of 50 mol % or more is used. Further, the average grain size of the silver halide grains is preferably 0.4 μm or less. Particle size follows the definition and measurement method described below. The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition distribution differs between the interior and surface layer of the grain, and the latent image may be It may be a particle that is mainly formed on the surface, or it may be a particle that is mainly formed inside the particle. In the light-sensitive material, silver halide grains may have any shape. One preferred example is one having a (100) plane as a crystal surface. In particular, silver halide grains having a ratio of (100) planes to (111) planes of 5 or more are preferred, and (100) planes may account for 100% of the grains. The (100) plane/(111) plane ratio of the particles can be measured by Kubelkamunk's dye adsorption method. In this method, a dye is preferentially adsorbed to either the (100) plane or the (111) plane, and the association state of the dye on the (100) plane and the association state of the dye on the (111) plane are spectrally different. Select and use. The (100) plane/(111) plane ratio can be determined by adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of the dye added.

The detailed ratio of (100) planes on the silver halide grain surface is as follows:
Tadaaki Tani, “Identification of crystal phase of silver halide fine grains in photographic emulsions using dye adsorption phenomenon,” Journal of the Chemical Society of Japan, 942.
~946 (1984). Preferred silver halide grains having a (100) plane/(111) plane ratio of 5 or more can be prepared by various methods. In general, the PAg value of the particle form is maintained at a constant value of 8.10 or less, and a silver nitrate aqueous solution and an alkali halide aqueous solution are simultaneously added at a rate that is faster than the dissolution rate of the particles and at which re-nucleation is large. It can be preferably prepared by the controlled double jet method. More preferably, the PAg value is 7.
The PAg value is preferably 80 or less, more preferably 7.60 or less. When silver halide grain formation is divided into two processes: nuclear shape and its length, there is no restriction on the PAg value when the nucleus shape is determined, and the PAg value at the time when the grain length is determined is preferably 8. 1
The value is preferably 0 or less, more preferably 7.80 or less, and still more preferably 7.60 or less. Also, the soluble root salt and soluble halogen salt may be reacted by a one-sided mixing method, but in order to obtain good monodispersity, a simultaneous mixing method is better. Also, U.S. Patent Nos. 4,183,756 and 4,225
, No. 666, JP-A-55-26589, JP-A-Sho. 5
Specifications such as No. 5-42737 and The Journal
of Photographic Science (J.Photo
gr. Sci). Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 21.39 (1973) and used. Furthermore, particles having twin planes may be used. The silver halide grains may be of a single shape or may be a mixture of grains of various shapes. Also, emulsions with any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions)
Alternatively, emulsions with a narrow particle size distribution (referred to as monodisperse emulsions) may be used alone or in combination.
Furthermore, polydisperse emulsions and monodisperse emulsions may be mixed and used. The silver halide emulsion may be a mixture of two or more silver halide emulsions that have been formulated separately. In the present invention,
Monodispersed emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. It is preferably at least 70%, particularly preferably at least 80%. Here, the average particle size r is the frequency n of particles having particle size ri.
Define the grain size ri when the product niXri' of i and ri3 is maximum. (3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image. The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the particle diameter or projected area on the print. (The number of particles to be measured shall be 1000 or more indiscriminately.) A particularly preferred highly monodispersed emulsion of the present invention is one having a degree of monodispersity of 20 or less, more preferably 15 or less as defined by be. Here, the average particle size and particle size standard deviation shall be determined from ri defined above. Monodispersed emulsions can be obtained with reference to Japanese Patent Application Laid-Open Nos. 5448521, 58-49938, and 60-122935. Although the photosensitive silver halide emulsion can be used as a so-called print live emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, G) afkides and Zel
IlHsan et al., or I1, Frieser
lJ4: Die Grundlagender Photo
graphischen Prozesse si
t Silberha1ogeniden, Ak
ades+icche Verlagsgesells
chaft, 196B) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metals, etc. can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in US Pat. No. 574.944, No. 2,410,689,
2.278,947, 2.728, 668,
It is described in No. 3,656.955. Examples of reduction sensitizers include stannous salts, amines, hydrazine derivatives,
Formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Patent No. 2,487.8.
No. 50, No. 2,419.974, No. 2,518.69
No. 8, No. 2,983.609, No. 2,983,610
No. 2,694.637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used. .448.060, British Patent No. 618,061. 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, particularly 5 to 8, and the PAg value is 5 to 11, particularly 7 to 9. It is preferable to keep it. In addition, the temperature is 40 to 90"C,
A temperature of 45 to 75°C is particularly preferable. In addition to the sulfur sensitization and gold/sulfur sensitization described above, the silver halide emulsion used can also be subjected to a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, etc. Below, as the margin photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed. In carrying out the present invention, for example, 4-hydroxy-6-methyl-1.3.3a. 7-tetrazaindene, 5-mercabuto l-phenyltetrazole,
Various stabilizers can also be used, including 2-mercabutobenzothiazole. Furthermore, if necessary, a silver halide solvent such as a thioether, or 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 are mixed with cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or Metal ions can be added using complex salts and included inside the particles and/or on the particle surface. Unnecessary soluble salts may be removed from the emulsion after the silver halide grains have been cured, or they may be left in the emulsion. When removing the salts, the method described in Research Disclosure No. 17643 can be used. The silver halide photographic material to which the present invention is applied may further contain a sensitizing dye. The dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobo-'lacyanine dyes, hemicyanine dyes, styryl dyes, and hemioxanol dyes. Particularly useful dyes include cyanine dyes, These pigments belong to merocyanine pigments and complex merocyanine pigments. For these pigments, any of the nuclei normally used for cyanine pigments can be applied as basic heterocyclic nuclei. Namely, pyrroline nuclei, oxazoline nuclei, Thiazoline nucleus, virol 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 aromatic hydrocarbon rings in these nuclei fused nuclei, i.e., indolenine nucleus, penzidolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, penzothiazole nucleus, naphthothiazole nucleus, penzoselenazole nucleus, penzimidazole nucleus, quinoline nucleus etc. These nuclei may be substituted with t on the carbon atom.

Merocyanine dyes or complex merocyanine dyes include a core with a ketomethylene structure, such as a birazolin-5-one core, a thiohydantoin core, and a 2-thioxazolidine-2 core.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, and the like can be applied. Sensitizing dyes can be used at concentrations equivalent to those used for ordinary negative-working silver halide. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. The amount of sensitizing dye per mole of silver halide is approximately 1. O XIO-' to about 5X10-' moles are preferred, and it is particularly preferred to use the sensitizing dye at a concentration of about 4X10-' to 2X10-' moles per mole of silver halide. The sensitizing dyes may be used alone or in combination of two or more. More specific examples of sensitizing dyes that can be advantageously used include the following. That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include those described in West German Patent No. 929,080, US Patent No. 2,231.658, and US Pat. 748
No. 2,503,776, No. 2,519. 00
No. 1, No. 2,912.329, No. 3,656,956
No. 3,672,897, No. 3,694.217, No. 4,025.349, No. 4,046,572,
British Patent No. 1,242.588, Japanese Patent Publication No. 1403/1973
No. 0, No. 52-24844, JP-A-48-731
Examples include those described in No. 37 and No. 61-172140. Further, as a sensitizing dye used in a green-sensitive silver halide emulsion, for example, US Pat.
39.201, 2,072.908, 2,73
No. 9,149, No. 2,945.763, British Patent No. 5
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent Publication No. 05,979 and Japanese Patent Publication No. 4B-42172. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
．． No. 269.234, 2, 270. 378, 2,442.710, 2,454. No. 629,
No. 2,776.280, Special Publication No. 17725, 1977,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in JP-A-50-62425, JP-A-61-29836, and JP-A-60-80841. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. A typical example is
U.S. Patent Nos. 2.688.545 and 2.977.22
No. 9, No. 3,397.060, No. 3,522.052
No. 3,527.641, No. 3,617,293, No. 3,628.964, No. 3,666.480,
3,672.898, 3,679.428, 3,703.377, 3,769.301, 3
, No. 814,609, No. 3,837.862, No. 4,
No. 026,707, British Patent No. 1.344.281;
It is described in Japanese Patent Publication No. 1.507.803, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Publication No. 110618-1980, Japanese Patent Publication No. 52-109925, etc. The silver halide photographic material to which the present invention is applied may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful. When dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer of the silver halide photographic light-sensitive material, 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 capri during the manufacturing process, storage or processing of silver halide photographic materials. That is, azoles such as penzothiazolium salts, nitroindazoles, triazoles, penzotriazoles,
Penzimidazoles (especially nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercabutothiazoles, mercabutobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercapto Pyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1.3.3a) , 7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc. Many compounds known as stabilizers can be added. An example of a compound that can be used is The Theory of the Photographic Process, by KJees.
Theory of the photography
c Process, 3rd edition, 1966), citing the original literature. For more detailed examples and other methods of use, see, for example, U.S. Patent No. 3.
954.474, 3,982.947, 4.0
You can refer to the description in No. 21,248 or Japanese Patent Publication No. 52-28660. Further, silver halide photographic light-sensitive materials have a photographic composition layer in U.S. Pat. No. 3,411,911, U.S. Pat.
The alkyl acrylate latex described in Japanese Patent Publication No. 45-5331 and the like can be included. The silver halide photographic material may contain various additives such as those described below. As thickeners or plasticizers, for example, U.S. Pat.
-63715, Belgian Patent No. 762,833, U.S. Patent No. 3.767.410, and Belgian Patent No. 588.143, such as styrene-sodium maleate Hardeners include aldehyde, eboxy, ethyleneimine, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carboxylic acid, mucochloric acid, acyloyl, etc. Various hardeners and ultraviolet absorbers include, for example, U.S. Patent No. 3.253.921 and British Patent No. 1.309,34.
Compounds described in each specification etc. of No. 9, especially 2-
(2'-hydroxy-5-tertiary butylphenyl)penzotriazole, 2-(2'hydroxy-3',5'-di-tertiary butylphenyl)penzotriazole. , 2-(
2-Hydroxy-3'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-
Hydroxy-3',5-di-tertiary butylphenyl)-5
-chlorobenzotriazole, etc.
Further, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent No. 548,532; 1,216.389, U.S. Patent No. 2.026.202, U.S. Patent No. 3,514.293
No., Special Publication No. 44-26580, No. 43-1792
No. 2, No. 43-17926, No. 43-3166, No. 4B-20785, French Patent No. 202.588, Belgian Patent No. 773. No. 459, Japanese Unexamined Patent Publication No. 48-
Anionic, cationic, nonionic or amphoteric compounds described in No. 101118 etc. can be used, among which anionic surfactants having a sulfonic group, such as succinic acid ester sulfonides,
Alkylbenzene sulfonated compounds are preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159, Japanese Patent Application Publication No. 4
8-89979, U.S. Pat. No. 2,882,15
No. 7, No. 2,972,535, Japanese Patent Application Laid-open No. 1972-20
No. 785, No. 4-43130, No. 48-90391, Special Publication No. 46-24159, No. 46-39312,
48-43809. - There are compounds described in each publication of No. 33627. When manufacturing photosensitive materials, the pH of the coating solution is 5.3 to 7.
A range of 5 is preferable. In the case of multilayer coating, it is preferable that the pH of the coating solution obtained by mixing the coating solutions 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 unfavorable, and if the pH is greater than 7.5, it may have an adverse effect on photographic performance, which is undesirable. The photographic layer of the light-sensitive material may contain matting agents such as silica as described in Swiss Patent No. 330,158, glass powder as described in French Patent No. 1,296,995, British Patent No. 1
, 173, 181; inorganic particles such as carbonates of alkaline earth metals or cadmium, zinc, etc.; US Pat. 322. 037, Belgian Patent No. 625,451 or British Patent No. 981.1
Starch derivatives described in No. 98, Special Publication No. 44-36
Polyvinyl alcohol as described in No. 43, Swiss Patent No. 3
30. No. 158, polystyrene or polymethyl methacrylate, U.S. Pat. No. 3,079,25
Polyacrylonitrile as described in No. 7, U.S. Patent No. 3.0
22. It may contain organic particles such as the polycarbonate described in No. 169. The photographic constituent layers of the light-sensitive material may contain slipping agents such as higher aliphatic higher alcohol esters described in U.S. Pat. No. 2,588.756 and U.S. Pat. 295,979, higher aliphatic calcium salts as described in British Patent No. 1.263.722, British Patent No. 1.313.384, U.S. Pat.
042,522 and 3.489.567. Dispersions of liquid paraffin can also be used for this purpose. The photosensitive material to which the present invention is applied may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1.
tea 17643 (December 1978) and 18
7, Vol. 1, Tea+ 18716 (November 1979), the silver halide photographic light-sensitive material is, for example, an emulsion layer and other photographic constituent layers, which are formed on one side of a flexible support commonly used in photographic light-sensitive materials. It can be applied to both sides. Useful flexible supports include films, baryta layers, or alpha-coated polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. Paper coated or laminated with olefin polymers (eg, polyethylene, polypropylene, ethylene/butene copolymers), etc. The support may be colored using dyes or pigments. It may be painted black for the purpose of blocking light. The surface of these supports may generally be treated with an undercoat to improve adhesion with emulsion layers and the like. Undercoat treatment is JP-A-52-1049
13, No. 59-18949, No. 59-19940, and No. 59-11941 are preferred. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. In silver halide photographic materials, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a force coating method, an extrusion coating method, etc. can be used. Next, the processing when processing the photosensitive material according to the present invention will be further explained. In the present invention, the photosensitive material contains 0.2 mol/2 or more of sulfite after being subjected to any suitable image exposure depending on the type of the material.p}19.0
The process is carried out using a developing solution of ~12.0 in the presence of a polyalkylene oxide compound and within 15 seconds, but the structure of the other steps is arbitrary. The preferred processing steps are:
It is important from the development, fixing, washing, and drying steps. In the present invention, when a black and white developer is used, a combination of dihydroxybenzenes and 1-phenyl-3-virazolidones is most preferable as the developing agent because it is easy to obtain good performance. Of course, it may also contain a p-anophenol developing agent. Examples of the dihydroxybenzene developing agent that can be used in the present invention include hydroquinone, chlorohydroquinone, promhydroquinone, isobrobylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2. 5-cyclotlOA troquinone, 2.
Examples include 3-:/7' romhydroquinone and 2,5-dimesylhydroquinone, with hydroquinone being particularly preferred. 1-phenyl-3 that can be used in the present invention
- As a developing agent for virazolidone or its derivatives,
l-phenyl-4,4-dimethyl-3-virazolidone,
■-Phenyl-4-methyl-4-hydroxymethyl-3
-virazolidone, l-phenyl-4,4-dihydroxymethyl-3-virazolidone, and the like. Examples of p-agonophenol-based developing agents that can be used in the present invention include N-methyl-p-agonophenol,
p-Aminophenol, N-(β-hydroxyethyl)
1-P-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-P-aminophenol, p
-Pendylaminophenol, among others, N-
Methyl p-a[nophenol is preferred. The developing agent is preferably used in an amount of usually 0.01 mol/l to 1.2 mol/l. Other additives that may be used in the copying fluid in the practice of the present invention include copying inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosol. , hexylene glycol, ethanol, methanol, and other organic solvents; I-phenyl-
Mercabut compounds such as 5-mercaptotetrazole, 2-mercaptobenzimidazu-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, penttriazole compounds such as 5-methylbenttriazole, etc. It may contain an anti-capri agent, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, an amino compound described in JP-A-56-106244, etc., if necessary. In the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-2434, can be used in the developer. In the present invention, the developing solution includes JP-A-56-10624
Amino compounds such as alkanolamines described in No. 4 can be used. Besides this, L. F.A. Mason, “Photographic
"Processin Chemistry", published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2.19.
No. 3.015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1973
- Those described in No. 64933 may also be used. In the present invention, "development time" and "fixing time" respectively refer to
When using an automatic processor, the time from when the photosensitive material to be processed is immersed in the developing tank liquid of the automatic processor until immersing in the next fixing solution, The time required for immersion in liquid). Furthermore, "washing time" refers to the time spent immersed in the washing tank liquid. In addition, "drying time" is usually 3 times when using an automatic processor.
The automatic developing machine is equipped with a drying zone where hot air of 5°C to 100''C, preferably 40°C to 80°C, is blown, and it refers to the time spent in the drying zone. Development temperature and The time is preferably 15 seconds or less at about 25°C to 50°C, more preferably 5 seconds to 15 seconds at 30''C to 45°C. The fixer is generally preferably an aqueous solution containing thiosulfate, with a preferred pH of 4.0.
Above, it is more preferably 4.2 to 5.5. Fixers include sodium thiosulfate and ammonium thiosulfate, but generally contain thiosulfate ions and ammonium ions, with ammonium thiosulfate being particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0.1 to 0.6 mol/7! It is. In the present invention, the fixing solution may contain an acidic hardener. In that case, various acid hardeners can be used in the fixer, such as water-soluble aluminum salts, chromium salts, and ethylenediaminetetraacetic acid complexes using trivalent iron compounds as oxidizing agents. You can use Preferred acidic hardeners are water-soluble aluminum ξnium salts, such as aluminum ξnium chloride, aluminum ξnium sulfate, potassium alum, and the like. The preferable addition amount is 0.01 mol to 0.2 mol;/ll, more preferably 0.03 to 0.2 mol/ll.
0.08-1-)L//l. In addition, tartaric acid, citric acid, or derivatives thereof may be used alone or in combination of two or more types in the fixing solution. Generally preferably, these compounds are used in an o. Those containing more than oos mole are effective, especially 0.0
1"e JLt/I!.~O..03 mol/l is particularly effective. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, Lithium citrate, ammonium citrate, etc. The fixing solution may optionally contain preservatives (e.g. sulfite, bisulfite), pH buffers (e.g. acetic acid, nitric acid), pH adjusters (e.g. sulfuric acid), It may contain a chelating agent having hard water softening ability or a compound described in Japanese Patent Application No. 60-213562. The fixing temperature and time are preferably about 20° C. to about 50° C. and 6 seconds to 1 minute, but 30° C. to about 50° C. It is more preferably 6 seconds to 30 seconds at 40°C, and even more preferably 6 seconds to 15 seconds at 30°C to 40°C. When a fixer concentrate is used and dilution water is used in type m, the fixer concentrate is It is most preferable that the solution is usually composed of an L agent. This is the same for the developing solution. A stock solution of a fixer as an L agent can exist stably, usually preferably at a pH of 4.5 or higher. Yes, more preferably p
H4.65 or higher. If the pH is less than 4.5, there is a risk that the thiosulfate will decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used. When the pH is in the range of 4.5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of the pH is not very strict, but if the fixation is carried out at too high a pH, the pH of the membrane will become high even after subsequent washing with water, and the membrane will swell, resulting in a large drying load, so a pH of up to 7 is desirable. When an aluminum salt is used as the acidic hardener in the present invention to harden the film, the pH is generally adjusted to 5.5 or less in order to prevent precipitation of the aluminum salt. In the present invention, it goes without saying that the developer and/or fixer may be a so-called working solution that does not require dilution water (that is, is replenished as an undiluted solution). When using concentrated liquids, the amount of each concentrated liquid supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrated liquid, but in general, the ratio of concentrated liquid to diluted water is is preferably in a ratio of 1:0 to 8, and the total amount of each of the developer and fixer is 50 -
Preferably, the number is 1,500 to 1,500. In a preferred embodiment of the present invention, the photosensitive material is developed and fixed, and then washed with water or subjected to stabilization treatment. For the washing or stabilization treatment, any method known in the art can be applied, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. For example, by using anti-mold water for washing or stabilizing liquid, not only is it possible to save water by requiring less than 3 Il of replenishment per 1 liter of photosensitive material, but it also eliminates the need for piping for installing an automatic processor. Furthermore, it is possible to reduce the number of stock tanks. That is, washing water (and dilution water for developer and fixer as necessary) or stabilizing solution,
It can be supplied from a single common stock tank, making it possible to further downsize automatic processors. If anti-mildew water is used in conjunction with washing or stabilizing liquid, the formation of lime scale can be effectively prevented, so for example, O~3J per bottle of photosensitive material.
! , preferably 0 to 1 liter of water can be saved. Here, when the replenishment amount is O, there is no replenishment at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservation water" is essentially not refilled. Refers to cases in which a processing method is used. As a method to reduce the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material in the fixer will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods. When washing with a small amount of water, patent application 1729/1986
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 Application No. 0-235133, it can also be used in a processing liquid having fixing ability, which is a processing step before that. This is more preferable because it saves the stock water and also reduces waste liquid.
Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the method using ion exchange resin described in JP-A No. 61-131632. Methods for purifying water using antibacterial agents as described in Japanese Patent Application No. 60-253807, No. 60-295894, No. 61-63030, and No. 61-51396 can be used. Furthermore, L. E. I1st “flater Qua”
ity Criteria" Photo Sci &
Eng. Vol. 9 Na6 (1965), M
J. Be-ach″Microbiological
Growths in l'lotion-Pic-L
ure Processing” SMPTt!Jo
urnal Vo1.85. (1976), R. O. D
eegan, ”Photo Processing
Wash Water Bio-cides” J.
Imaging Tech. Vol 10. Na6(
1984) and JP-A No. 57-8542, No. 57-
No. 58143, No. 5B-105145, No. 57-13
No. 2146, No. 58-18631, No. 57-9753
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 0, No. 57-157244, etc. can also be used in combination. Furthermore, in the washing bath, R. T. Written by Kreisan J. Im
age. Tech10. (6) 242 (1984)
Isothiazoline compounds described in Research Disclosure Vol. 205, Summer tes 20526 (19
Isothiazoline compounds described in Vol. 228, Item 22845 (April issue, 1983); Compounds described in Japanese Patent Application No. 1983-51396; Can also be used together as a microbiocide. Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloracetate, p-hydroxybenzoic acid ester, 2-
(4-thiarizone)-benzimidazole, penzisothiazolin-3-one, dodecyl-penzyl-dimethylammonium chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4.4'trichloro-2'-hydroxydiph There are enyl ethers, etc. The amount of water kept in a water stock tank with anti-fungal measures added as dilution water for the processing solution stock solution such as the developing solution and fixing solution is preferably 0.01 to 10 g/l, more preferably 0.
．． 1~5 g/j! It is. Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in the ``Surfactant Handbook'' published by Kogaku Tosho ■. Various compounds can be added to the above stabilizing bath for the purpose of stabilizing the image. For example, adjust the membrane pH@tli (for example, p
H3-8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination with acids, etc.) and formalin. In addition, cleaning agents, disinfectants (thiazole-based, isothiazole-based, halogenated phenols, sulfanilamide, penzotriazole, etc.), surfactants,
Various additives such as optical brighteners and hardeners may be used, and two or more compounds for the same or different purposes may be used in combination. In addition, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as membrane pH adjusters to the processing solution in order to improve image storage stability. The water washing or stabilization bath temperature and time in the above method is preferably 5 seconds to 30 seconds at 0°C to 50°C, more preferably 5 seconds to 20 seconds at 15°C to 40°C, and more preferably 15°C to 40°C. 5 seconds to 0 seconds is preferable. In the practice of the present invention, a method may be used in which 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 about 4
It can be carried out at a temperature of 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 1 minute, but it is more preferable. This will be explained in detail. However, as a matter of course, the present invention is not limited to this. Example l In the presence of water-soluble iridium 2XIO-' mol/silver 1 mol and water-soluble rhodium 4X 10-' mol/silver 1 mol, the odor was Silver chlorobromide grains containing 30 mol% of silver oxide were obtained.
These particles were cubic grains with an average particle size of 0.24 μm, and the width of the particle size distribution was 11%, (100 faces)/(11
The ratio of 1 page) was 95/5. Add 1 silver halide to this
After gold sensitization and sulfur sensitization by adding 0.6 g of potassium bromide per mole, the following sensitizing dye <A> was added, and 4-hydroxy- as a stabilizer was added per mole of silver halide.
6-methyl-1.3,3a. Ig 7tetrazaindene
In addition, 700 mg of the following compounds (B>, 600 mg of sodium n-dodecylbenzenesulfonate, 2 g of styrene-maleic acid copolymer, 3 g of ethyl acrylate polymer latex were added, and a polyethylene terephthalate film was added. A silver halide emulsion layer was coated on top with a silver content of 3.5 g/nf and a gelatin content of 1.8 g/rd. 30g+g/% of sodium 1-decyl-2-(3-isobentyl)succinate-2-sulfonate as a spreading agent, and 30g/% of 1-hydroxy-3.5-dichlorotriazine sodium salt as a hardening agent.
A protective layer containing formalin 25%/ffr was coated in multiple layers on the film on which the packing layer had been applied in advance. As a result, a sample was obtained which had an emulsion layer and a surface protective layer on one side of the support and a packing layer on the opposite side (Sample Hiro1). In contrast to the above comparative sample ttl, samples M2 to
10 (sample according to the present invention) was obtained. <A>(B> Each sample obtained was screened with a contact screen (gray negative 1
50L), an optical wedge and an interference filter of 680, using a xenon flash for 10 seconds, using a roller type automatic developing machine under the following conditions, and evaluating the halftone dot quality. In addition, the Tsunaten Award was evaluated in 10 stages. 10 is best, 1-4 is unusable, 5
This is the usable level. Development unevenness and sensitivity were evaluated as follows. From Table 1, it can be seen that the product according to the present invention has no uneven development, high sensitivity, and good bond quality. <Developer prescription> (Group A) Pure water (ion exchange water) 150m ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (
55% w/v aqueous solution) 100af potassium carbonate 50g hydroquinone
15g 5-Methylbenzotriazole 100■L-Phenyl-5-mercaptotetrazole 30Potassium hydroxide Amount to bring the pH of the solution to 10.4 Potassium bromide 4.5g (Kumii B) Pure water (ion exchange water) Diethylene glycol ethylene diamine tetraacetic acid dinaacetic acid (90% aqueous solution) 5-Nitroindazole 1-phenyl-3-birazoli compound <C> 3-50g Thorium salt 25■ 0.3ml 110■ Don 700■ 80IIg Water 500ml when using developer The above group A and group 7iB are inside.
Dissolved in this order and made up to 1 liter for use. Fixer formulation> (formation A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0m Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g Sodium citrate dihydrate 2g Acetic acid (90% -/V aqueous solution) 13.6m (Kumii B) Pure water (ion exchange water) 17 Monosulfuric acid (50% -/V aqueous solution) 4.7g
Aluminum sulfate (aqueous solution with a calculated content of 8.1%) 26.
5 g When using the fixer, add the above &! I-Kai A and Kumi-Kai B were dissolved in the order of "If" and used as a fixing solution. The pH of these fixers was approximately 4.5. Each process of the automatic developing machine is as follows. Development 38
°C 12 seconds fixing 38 °C 10 seconds washing 20 °C 10 seconds drying 60 °C Dry to Dry processing time 48 seconds Table 1 [Effects of the Invention] According to the present invention, the conventional problems are solved and there is no uneven development. It is possible to provide a method for processing a silver halide photographic material, which has high sensitivity and can also achieve high contrast of images.

Claims (1)

[Claims] 1. After image exposure, a silver halide photographic material having at least one silver halide emulsion layer on a support has a pH of 9.0 to 12.
1. A method for processing a silver halide photographic light-sensitive material, which is characterized in that the processing is carried out in the presence of a polyalkylene oxide compound using a 0.0% developer for a developing time of 15 seconds or less.