JPS60263146A - Formation of image - Google Patents

Abstract

PURPOSE:To obtain an image low in fog, and high in dot quality and contrast by processing a silver halide photographic sensitive material with a specified developing soln. in the presence of a polyalkylene oxide compd. CONSTITUTION:The silver halide photographic sensitive material contg. at least 50mol% silver chloride is processed in the presence of a polyalkylene oxide compd. and/or its deriv. with a developing soln. contg. phosphate, a hydroxybenzene type developing agent, sulfite ions at least in a concn. of 0.2mol by 1l of the developing soln., and a compd. represented by the formula (R1 is nitro, R2 is H or 1-3C lower alkyl, and M is a cation, such as H, alkali metal, alkaline earth metal, or ammonium), such as 5- or 6-nitroindazole or each alkali metal salt, and having a pH of >=11. As the developing agent, hydroquinone is practicable, and as the source of said sulfite ions, sodium sulfite and potassium bisulfite, etc., are enumerated.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for forming a high-contrast silver image by processing a silver halide photographic light-sensitive material, and in particular to a method for processing a silver halide photographic light-sensitive material used in the field of graphic arts. The present invention relates to an image forming method for producing high-contrast images in which a rapid developing solution containing a higher concentration of sulfite is used to process a sulfite (hereinafter abbreviated as "photosensitive material") than the developer solution used.

(Prior Art) Lith developer contains a dihydroxybenzene compound as a developing agent, has a pH in the range of 9 to 11, usually 95 to 10.5, and contains a low concentration of sulfite (usually 0.5 to 10.5) as a preservative.
1 mol/l or less), formalin and bisulfite adduct (
It is characterized by containing sulfite ion) and 7A.

Regarding the method of forming such high-contrast photographic images and Lith developer, please refer to J.C. Neil, Journal of the Franklin Institute (J.
,A.C.,Yule ,I”J,of the Fra.
nklinInst, j volume 239, page 221 (19
45).

Incidentally, lithographic development is sometimes called contagious development because development occurs contagiously.

When performing Lith development processing, high contrast and high quality halftone dots can be obtained, but as can be inferred from the characteristics of the Lith developer described above, there are problems with air oxidation, storage stability and rapid processability. be. In this sense, stabilization and acceleration are old and new themes in the field of graphics and art.

Rapid processing here means development time of less than 1 minute, usually 40
Refers to processing within seconds.

Examples of rapid processing methods from the developer side include high-pH 1 high-temperature development, and the combination of a dihydroxyben-based agent and a developing agent that exhibits superadditivity (for example, l-phenyl-3-pyrazolidone-based developing agent). However, when taken alone, these methods conflict with stability or contrast enhancement, which is currently the biggest problem when rapidly processing light-sensitive materials.

As a method to improve the above problems, JP-A-53-177
No. 20, No. 54-92235, No. 56-106244
There are numerous technical disclosures, such as issues. However, neither of these has reached a satisfactory level, and still
Higher quality and faster processing are strongly desired.

(Object of the Invention) Accordingly, the first object of the present invention is to provide an image forming method for obtaining high-contrast images with rapid processing, and the second object of the present invention is to provide high-quality halftone dots with low capri. The object of the present invention is to provide an image forming method, and the purpose of the third aspect is to provide an image forming method that is stable, rapid, and quick-processing.
The object of the invention is to provide an imaging method that produces images with less silver sludge.

(Structure of the Invention) The object of the present invention is to provide a silver halogenide photographic light-sensitive material having a silver halogenide composition containing at least 50 mol% of a chloride complex, a polyalkylene oxyphosphate and the following components. p can be achieved by an image forming method in which processing is performed with a developer having a pH of 11 or higher.

Ingredient-+11 Dihydroxybenzene-based developing crude drug ingredient-
(2) Sulfite ion component with a concentration of at least 0.2 molar per developer 11 - (3) Compound represented by the following general formula [1] General formula (1) In the formula, R1 is a nitro group, R1 is a hydrogen atom or 01~C,
represents a lower alkyl group. M represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an ammonium ion.

The components of the developer used for processing the photosensitive material according to the present invention will be described in detail below. Contains the compound shown in

The compound represented by the general formula [1] used in the present invention (
Hereinafter, it will be referred to as the compound of the present invention [1]. ) is an example of
Examples include 5-nitroindazole, 6-nitroindazole, and alkali metal salts thereof, and these may be used alone or in combination. The concentration range of the compound [I] of the present invention is 1 g to 1 g, preferably 1
'Oda~300~. A density outside this range is unfavorable in terms of manufacturing cost and photographic performance.

The compound [1) of the present invention may be dissolved in an organic solvent and added, or may be added directly, and is not taken in that form. Examples of the organic solvent include triethylene glycol, diethylene glycol, jetanolamine, triethanolamine, methanol, and ethanol.

The developing agent used in the developer according to the present invention is a dihydroxybenzene-based developing agent, and can be appropriately selected from p-dihydroxybenzene-based developing agents well known in the field of photography. Specific examples thereof include hydroquinone, chloronohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroxy/2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone sulfonate. Among these, hydroquinone is particularly practical. These developing agents may be used alone or in combination. The amount of developing agent added is 5 to 509 per 11 developer solution,
A sulfite salt can be used as a source of sulfite ions in the developer according to the present invention, preferably having a modulus of 10 to 30.9. Sulfite is sulfite ion < So
, ”) may be used, including sodium sulfite, potassium sulfite, potassium bisulfite, etc.

The concentration range of sulfite ions may be 90.2 moles or more per 11 parts of the developer, but a concentration of 1 mole/1 or more is not practical for production. The preferred concentration range is 0.4 mol/l to 0.7 mol/l.

The pH range of the developer according to the present invention is pH 11 or higher,
If the pH exceeds 13.5, it is dangerous to handle and there is no particular advantage. Further, a pH of less than 11 is unfavorable in terms of photographic performance.

For the above pH adjustment, sodium hydroxide, potassium hydroxide,
Alkali commonly used in the field of photography, such as potassium carbonate and sodium carbonate, are used.

The developer according to the present invention contains a phosphate, but the phosphate used in the present invention only needs to become a phosphate in the developer, and may be in any form when used, for example, phosphoric acid,
Examples include sodium phosphoric acid/hydrogen, sodium phosphate, potassium phosphate, polyphosphate, and the like.

The photosensitive material according to the present invention is processed in the presence of a polyalkylene oxide compound and/or a derivative thereof using a developer having the composition described in detail above.

Next, the above-mentioned polyalkylene oxide compound used in the present invention refers to a compound containing at least 10 or more and at most 200 or less polyalkylene oxide chains in the molecule, such as polyalkylene oxide, aliphatic alkonyl, phenol, etc. , aliphatic mercaptans, organic amines, ethylene oxide, propylene oxide, etc. by condensation reaction with compounds having active hydrogen atoms such as fatty acids, aliphatic mercaptans, organic amines, or polyols such as polypropylene glycol, polyoxytetramethylene polymers, etc. It can be synthesized by condensing. The above polyalkylene oxide compound may be a block copolymer in which the polyalkylene oxide chain in the molecule is divided into two or more locations instead of one. At this time, the total polymerization degree of the polyalkylene oxide is preferably 10 or more and 100 or less.

Specific examples of the polyalkylene oxide compound used in the present invention are shown below, but the present invention is not limited thereto.

[Exemplary compounds]

(2-1) HO(CH, CH, OnnH (n=35)
(2-2) n-C,H,0(CH,CH,O)AIH
(/=20) (2-3) n-C,H,,0(CHIC
H, ON IH (A!=30.:1(2-4) n-C,
tHuo(CHtCHzO) IH(1=303[2-
6) n-C+tHtsS(CHzCHzO)/HCl
=301(2-7) C4H,5(CH,CH,0)n
cOcH, CH2C0OH [n=50] [2-8) H
O(CH,CH20)l(CHt)m(CHtCHtO
)nCOCH,CH,C00H(A!+n=70.m=
5)(2-9) HO(CH,CH,0)7(CHCH
,O)m(CH,CH,0)nHCH3 [7+n=15 ,F17:] (210) HO(CH2C0OHminCHCH,O)
m(CHzCHzO)nHCH8 (#-1-n=30, F35) [2-11) HO(CH,CHtO)J? (CHCH
ffiO)m(CHtCHtO)nH0! Eight [/+n=15, m=15. ) C2-12) HO(CH,CH,0)7(CHCH,O
)m(CH,CMtO)nHC,H.

[A'+n=30, m=15) [2-13) HO(CH,tl(,0)l(OH,CH
,CH,C1-1,0)m-(CH,CMtO)nH(
At+n=23. rry21 ) [2-14,]
HO(CI-1,CH20)l(OH,Cl-1,CH
,CH,O)m-(CH,CH,0)nHIJ+n=3
+8, rF15)(2-15)HO(CH,CH,0
)l(CHCH,O)m(CH,CH,0)nH0H,
QC Peng (/+n=15, m=15) [2-16) HO (CI, CH, 0) AI (CHCH,
O)m(CH,C1-1,0)nH(J(,OCH.

[A'+r+-30, m-15) (2-17)n-C,IH,0(CHCHtO)l(C
H, CHtO) m8 formula % formula %] ) ) ) ( ) :] In the present invention, the amount of the optionally used polyalkylene oxide compound added is 11% of the developer solution.
The amount is 40 g, preferably 0.1 g to 5 g. As for the addition method, it may be added after being dissolved in water or triethylene glycol, or it may be added as is. When a polyalkylene oxide compound is saturated in a light-sensitive material, the amount per mole of silver halide is 0.01 to 10. lit is preferably in the range of 0.1 g to 3 g. The addition position may be in the silver halide emulsion layer and/or the non-photosensitive layer, but is preferably in the silver halide emulsion layer and/or the layer below it.

According to a preferred embodiment of the present invention, the photosensitive material according to the present invention to be processed by the above-described method of the present invention preferably contains a tetrazaindene compound.

Typical specific examples of the above tetrazaindene compounds include:
Mention may be made of 4-hydroxy-6-methyl-1,3,3a17-tetrazaindene.

According to another preferred embodiment of the present invention, the photosensitive material according to the present invention preferably contains a metal salt of Group 8 metal. Examples of the above Group 8 metal salts include platinum chloride, hexahalogenoiridium complex salts, water-soluble rhodium salts, etc. Particularly, water-soluble rhodium salts include rhodium dichloride, rhodium trichloride, hexachlorodium salt, etc. Examples include ammonium acid, and preferably a complex compound of rhodium trichloride and a halogen, preferably chlorine or bromine. The amount added is silO'''5-1O-s molte alkali, 10'''4-1O-s per mole of silver halide.
-s mol is more preferred. If the amount of the water-soluble rhodium salt exceeds 10-'', the object of the present invention cannot be achieved because the tone becomes soft, although there is still a tendency to desensitize.On the other hand, if the amount is less than 101 mol, the object of the invention cannot be achieved The sensitivity cannot be lowered to the level required for use in a bright room, which is one of the reasons, and the purpose cannot be achieved.

According to yet another preferred embodiment of the present invention, the photosensitive material according to the present invention has a gelatin coating amount of 3 on the photosensitive layer side.
It is preferable that it is 9/d or less, and the amount of gelatin attached is 3
17/n? In particular, the rapid processing properties are improved if:

According to yet another preferred embodiment of the present invention, the developer according to the present invention preferably contains an organic solvent.

Organic solvents used in the present invention include diethylene glycol, triethylene glycol, tetraethylene glycol, triethanolamine, jetanolamine, and the like. The amount added is 9109 g or more per 11 g of the developer, preferably 20 to 100 g. If it exceeds 200g, it is not economical.

Furthermore, according to another preferred embodiment of the present invention, the concentration of sodium ions (Na"l) in the developer according to the present invention is
and potassium ion concentration CK”:] ratio (Na +]
/(K'') is preferably at least 1, which improves halftone dot performance.

According to yet another preferred embodiment of the present invention, the developer according to the present invention preferably contains a compound represented by the following general formula [■], whereby even better results can be obtained.

General formula [1] In formula C, zH represents a heterocycle containing a nitrogen atom.

M represents the same meaning as in general formula (1). '] In the general formula [Dan], the heterocycle represented by Z is preferably a 5- to 6-membered heterocycle which may be fused with a benzene ring,
Examples include oxazole, benzoxazole, thiazole, benzothiazole, triazine, pyrimidine, tetrazaindolizine, triazaindene, and purine.

Further, the heterocycle may have a substituent other than the 18M group described in the general formula [...], and examples of the substituent include a halogen atom, a sulfo group, a hydroxyl group, a lower alkyl group, a phenyl group, etc. can be mentioned.

General formula [
Specific examples of the compound represented by 1) are shown below, but the invention is not limited thereto.

[Exemplary compounds]

(3-1) C3-2] The amount of the compound represented by general formula (1) is
nsw-1jis is preferably 10#-500 or higher.

The mechanism of the present invention is that the conventional developing solution utilizes a developing agent, and therefore it is estimated that the developing solution is effective in a pH range of 11 to 13.5. In this pH range, current herbal medicines are very active, usually generate capri, become soft in tone, easily generate silver sludge, and have very poor storage stability over time, making them completely impractical.

However, according to the present invention, in this high pH region, a compound having a sulfite ion concentration of at least 0.2 molar per developer iz, a compound represented by the general formula (1), a polyalkylene oxide compound, a phosphate and When/or an organic solvent was used in combination, it was possible to suppress capri very effectively, increase contrast, reduce silver sludge, and maintain stability and high activity. Theoretical elucidation of this mechanism is not complete, but the stabilizing effect of high concentrations of sulfite ions and organic solvents (it seems that these effects are not the same), sulfite ions and the compound represented by general formula (1) This is presumed to be due to a complex synergistic effect such as the interaction of dissociated substances and the stabilizing effect of phosphate.

Furthermore, when the compound represented by the general formula [11] was used in combination, silver sludge could be significantly reduced.

In addition to the above-mentioned compounds, the developer according to the present invention includes an auxiliary developer such as 17x nyl-3-pyrazolidone to an extent that does not inhibit the contrast enhancement effect, a water-soluble acid such as acetic acid or boric acid, potassium carbonate or borax. pH buffering agents such as potassium bromide,
Fog suppressants such as potassium iodide, 5-methylbenztriazole, 5-nitrobenzimidazole or 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, ethylenediaminetetraacetate or nitriloacetic acid; It may contain a water softener, an antioxidant such as ascorbic acid, ethylene urea or kojic acid, a development accelerator such as 4R ammonium salt, a nucleic acid decomposition product such as adenine or guanine, and the like. It is preferable not to contain formalin-generated products such as formalin-bisulfite adducts contained in the Lith developer.

The silver halide used in the silver halide photographic emulsion of the light-sensitive material processed with the developer according to the present invention includes silver chloride,
Silver chlorobromide, silver chloroiodobromide and silver chloroiodide are used,
In either case, it is preferable that the silver chloride content is 50 mol% or more, particularly 70 mol% or more.

The emulsion used in the present invention can be prepared by any of forward mixing, back mixing, manual mixing, and simultaneous mixing, but the most preferred method is simultaneous mixing.

Methods for preparing emulsions include an ammonia method, a neutral method, and an acidic method, and it is preferable to use the neutral method or the acidic method.

The distribution of silver halide grains in the emulsion may be either monodisperse or heterodisperse, but monodisperse is preferable for uniform grain sensitivity. Further, the grain crystal habit may be cubic, octahedral, dodecahedral, spherical, or any other shape.

The particle size is preferably 1μ or less, preferably 0.5μ or less. More preferably, the thickness is 0.3μ or less. This is because it is necessary to make the grains finer in order to prevent the developing silver grains from becoming rough and to save resources, in order to achieve the required photographic density with a small amount of silver.

The emulsion thus prepared is chemically sensitized (e.g. sulfur sensitization, gold-sulfur sensitization, reduction sensitization, etc.) using a chemical sensitizer.
do. However, if the light-sensitive material according to the present invention is a bright-room light-sensitive material, no chemical sensitization is required.

Chemical sensitizers used in the above chemical sensitization include, for example, active gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N , N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, ditin chloride, etc.), such as potassium chlorooolite, potassium aurithiocyanate, potassium salt
Various noble metal sensitizers such as rooleate, 2-oresulfopenzothiazole methyl chloride, ammonium chloroparatate, potassium chloroplatinate, sodium chloroparadite, etc. are used alone or in combination of two or more. be able to. When using a gold sensitizer, KO Danammon can also be used as an auxiliary agent.

Further, the silver halide emulsion used in the present invention is, for example, U.S. Pat. No. 2,444β07, U.S. Pat.
, No. 512,982, West German Application Publication No. 1,189.38
No. 0, No. 2ρ58β26, No. 2U18.411, Special Electric Power No. 11843-4133, U.S. Patent No. 3342596, Japanese Patent Publication No. 47-4417, West German Application Publication No. 2,149
, No. 789, Special Publication No. 39-2825 and Special Publication No. 49-
13566, preferably, for example, 5,6-drimethylene-7-hydroxy-s-)riazolo(1,5-a)pyrimidine, '5.6-fh□
fv7-7-t#,”. Yatu 3-triazolo (1,5
-a) Pyrimidine, 5-methyl-7-hydroxy-8-
) Riazolo(1,5-a)pyrimidine, 7-hydroxy-8-triazolo(1,5-a)pyrimidine, 5-methyl-6-promoerhydroxy-8-to! J Azolo (
l.

5-a) Pyrimidine, gallic acid ester (e.g. inamyl gallate, dodecyl gallate, propyl gallate,
Mercaptans containing gallic acid sodium (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benztriazoles (5-bromobenztriazole, methylbenztriazole), benzimidazoles (6-nidrobenzimidazole), etc. It can be stabilized using In addition, the silver halide emulsion used in the present invention includes, for example, West German Application Publication No. 2.21
It is also possible to use latent image stabilizers such as the money-saving amino acid compounds described in No. 7,153 and No. 2,217,895.

Particularly preferably, when 1-phenyl-5-mercaptotetrazole is used in combination, the amount added is 1 mol of silver halide, preferably 1 to 511 s, and 10 to 500 mol of silver halide.
It's da.

In addition to the above-mentioned additives, the silver halide emulsion described above may contain additives such as
Optical sensitization to a desired wavelength range can be achieved by using optical sensitizers such as cyanine dyes and merocyanine dyes alone or in combination.

Furthermore, the silver halide emulsion described above may contain a cover link power improver, an injector inhibitor, a wetting agent, a latex, a polyalkylene oxide, a spreading agent, a hardening agent, and the like.

The hydrophilic colloid particularly advantageously used in the emulsion layer of the light-sensitive material used in the present invention is gelatin, but examples of hydrophilic colloids other than gelatin include colloidal albumin, diaphragm, gum arabic, and 7 A acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, e.g. British Patent 523,66
No. 1, West German Application Publication No. 2,255,711, No. 2,0
46,682, U.S. Pat. No. 3,341,332, etc., gelatin glass conductors, such as U.S. Pat.
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Pat. No. 53, etc., or U.S. Pat.
Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, and methacrylic ester as described in No. 1. D can also be applied to hydrophilic colloid layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

In the present invention, when coating an emulsion layer, the amount of coated silver is
Silver, usually 0.1 g ~ 101/m s Ff
Mashukuke, II~5, li'/trt. In that case, gelatin as the preferred hydrophilic colloid is
0.1! l''10 g/trj, particularly preferably IF~59/d.

The photosensitive material according to the present invention is arranged on a suitable photographic support, and examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polyjapyrene synthetic paper,
Typical examples include glass paper, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. It is selected as appropriate depending on the purpose of use.

The photosensitive material according to the present invention is typically formed by coating on a support at least one hydrophilic colloid layer containing the silver halide according to the present invention. It is desirable that a gelatin protective layer having an appropriate thickness, preferably 0.1 to 10μ, particularly preferably 0.8 to 2μ, be applied to the protective layer.

The hydrophilic colloid layer including the emulsion layer used in the present invention may optionally contain various photographic additives such as hardeners, surfactants, image stabilizers, ultraviolet absorbers, anti-stain agents, p.
H regulator, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener, current speed v4 adjuster,
It is possible to use matting agents and the like within a range that does not impair the effects of the present invention. For example, as a thickener or plasticizer, U.S. Pat.
63715, Japanese Patent Publication No. 45-15462, Belgian Patent No. 762,833, U.S. Patent No. 3,767,410, Belgian Patent No. 558.143, etc., such as styrene-sodium maleate copolymer Examples of hardening agents such as dextran sulfate include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based,
Various hardeners such as vinyl sulfone type, incyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, and acyloyl type can be used in the hydrophilic colloid layer including the emulsion layer of the photosensitive material used in the present invention. can.

Although the present invention has been described in detail above, the object of the present invention can be achieved by the present invention. Next, this will be demonstrated by examples, but the present invention is not limited to the examples.

Example 1 0.2μ cubic crystal monodisperse silver chloroiodobromide (silver chloride composition: 80 mol%) was prepared according to a conventional method, and after gold-sulfur sensitization,
2-methyl-4-hydroxy-1゜3, 3a, 7
-tetrazaindene (39/silver 1 mole), 1-(β-hydroxyethyl)-3-phenyl-5-((3-r-sulfobutyl-α-penzoxazinonidene)-ethylidene cothiohydantoin (200 1 mole of silver), 1-phenyl-5-mercaptotetrazole (10~/1 mole of silver), 3% saponin as a coating aid, polyethyl acrylate as a softener, exemplified polyalkylene oxide compound (2-5) ( 600M9/1 mole of silver), the amount of gelatin in the emulsion layer was 29/m, and the amount of silver was 3.51/m.
Gelatin was added so as to give the following protective layer solution on a polyester base, and the mixture was coated in a multilayer at the same time as the following protective layer solution and dried. The above protective layer solution contains gelatin, succinic acid octyl ester as a coating aid, 4 μm of silica as a matting agent, 1 silica as a matting agent, 2-hydroxy-4,6-dichloro-1,3,5- as a hardening agent.
) It consists of riazine sodium salt, etc., and as mentioned above, the amount of gelatin attached is 2. ! It was simultaneously coated on the emulsion layer so as to have a ratio of i'/m and dried.

The coated sample obtained above was cut into an appropriate size, exposed to light through a wedge using a plate-making camera, and developed with a developer having the composition shown below. When evaluating halftone dot quality, exposure was further carried out using a commonly used contact screen, the development conditions for evaluation were 38°C for 20 seconds, and fixation was carried out using a normal fixing solution that did not use an acid hardener. .

Developing Solution Composition 1 (Developing Solution-1) (Developing Solution-2) A composition obtained by removing potassium phosphate from Developer-1 and adding the same mole of potassium carbonate (Developing Solution-3) From Developer-1 A composition in which potassium phosphate is removed and the same molar amount of sodium borate is added (Developer-4) A composition in which the concentration of potassium phosphate in Developer-1 is 0.17 l/l and a composition of 9 (Developer- 5) The concentration of potassium phosphate in gt liquid-1 was 1.07 l/I.
t ('fjL imager solution-6) Developer solution-4 with 065 moles of potassium carbonate added (Developer solution-7) Developer solution-1, excluding potassium phosphate, and the same mole of potassium silicate The results obtained are shown in Table 1 below.
It is evaluated at a point indicating a concentration of 3.0 on the I&D characteristic curve and is expressed as relative sensitivity. It is also displayed including the Kabu VH base concentration. The gradation is indicated by the slope of the straight line on the characteristic curve, and the quality of the halftone dots was visually determined using a 100x magnifying glass, and was relatively graded in 10 steps. (and 10
Table 1: Samples of the present invention in which the photosensitive material of the present invention was rapidly processed using a phosphate-rich developer had excellent halftone dot quality, and The tonality is good, and there is no deterioration in sensitivity or fog, and it is possible to obtain a high-contrast image that is far superior to that of the comparative sample.Example 2 In the same manner as in Example 1, the average grain size was 0. A 3μ silver chloroiodobromide emulsion (silver chloride: silver bromide: silver iodide - 90:90:1) was prepared and sensitized with sulfur, followed by anhydrous 5.5-μm as a sensitizing dye.
Dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt (2501R9/silver 1 mol), exemplified polyalkidine oxide compound (2-14) (400 Da/silver) 1 mole)
, and other additives were added in the same manner as in Example 1 to prepare an emulsion and a protective layer solution, which were coated onto a support and dried. The obtained coated sample was exposed in the same manner as in Example 1, treated with a developer having the following composition, and evaluated.

- Developer solution composition - (Developer -8) (Developer -9 - Developer solution -8 with pH adjusted to 12.5 (Developer -
10) Developer solution-8 with pH adjusted to 11 (Developer solution-11
) Developer solution-8 with pH adjusted to 10 (Developer solution-12
) Developer solution-8 in which the sodium phosphate was replaced with the same molar amount of sodium carbonate (Developer solution-13) Developer solution-8 in which 100 μ of exemplified compound (3-1) was added (Developer solution-14) In the above table, evaluation of silver sludge is based on visually observing the silver sludge produced by processing a certain amount of unexposed film in developer No. 17. This is a five-level evaluation. (5 was considered the best) From the results in the above table, it can be seen that the photosensitive material according to the present invention is developed by containing a phosphate or a compound represented by the general formula (II) together with a phosphate, and having a pH of 11 or more. It can be seen that the samples of the present invention treated with the liquid have improved gradation and halftone dot quality without deteriorating the sensitivity capri compared to the comparative samples, and also have good effects on silver sludge.

Example 3 0.15μ monodispersed silver chlorobromide agent (silver chloride:bromide chain=99
:1) was prepared in the presence of rhodium chloride (104 mol/mol silver), 2-methyl-4-hydroxy-1,3,3a,7-tetrazaindene (211/mol silver) as a stabilizer, l-Phenyl-5-methylcaptotetrazole (150~/1 mole of silver), exemplified polyalkylene oxide compound (2-10) (9oOw/1 mole of silver), 2% Suponin as a coating aid, polyethyl as a softener. Add gelatin to acrylate (#1 such as 100 weight XL) so that the gelatin coating amount of the emulsion layer is 1.8 g/m and the silver coating amount is 311/l, and apply the following composition onto the polyester paste. A multilayer coating was applied simultaneously with the protective layer solution and dried.

That is, the protective layer liquid contains gelatin, phthalated gelatin, 2X saponin, polymethyl methacrylate with an average particle size of 3 μm, 2-hydroxy-4,6-dichloro-1,3,
It contained 5-triazine sodium salt, etc., and was simultaneously coated on the emulsion layer so that the gelatin coverage was 21/d as described above.

The above-mentioned coated sample was exposed in the same manner as in the above-mentioned example and treated with the developer shown in the table below, and the results obtained are shown in Table 3 below.

Table 3 As shown in the table above, the samples of the present invention, in which the photosensitive materials of the present invention were quickly processed with a developer containing phosphate, showed no deterioration in sensitivity or fog, and the image quality was improved. In terms of tonality, it can be seen that the halftone dot product 'J[ is improved.

(Effect of the invention) A silver halide photographic light-sensitive material containing a silver halide composition containing at least 50 mol% of silver chloride is heated to pH 1 containing a phosphate in the presence of a polyalkylene oxide compound.
By processing with one or more rapid developers, photographic properties,
In particular, the halftone quality, gradation and silver sludge are significantly improved without deteriorating the sensitivity and capri.

Agent: Patent Attorney No. 1) Step-parent procedure amendment March 13, 1985 Manabu Shiga, Commissioner of the Patent Office 1. Indication of the case 2. Name of the invention Image formation method 3. Person making the amendment 1! Relationship to the matter Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-5 Sakura-cho, Hino-shi, Tokyo 191 Japan Subject of amendment "Detailed description of the invention" column J of the specification
6. Amendment 0 Contents 1) Page 33 of the specification, line 3, “Silver iodide = 90:90J” [Silver iodide = 90:9J
I am corrected.

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Claims (7)

[Claims] (1) A silver halide photographic light-sensitive material having a silver halide composition containing at least 50 mol% of silver chloride, containing a phosphate and the following components, in the presence of a polyalkylene oxide compound and/or its derivatives: pH
is 11 or more 311! An image forming method characterized by processing with e-liquid. Ingredients - (1) Dihydroxybenzene developing agent ingredient -
(2) Developer solution 1, a sulfite ion component with a concentration of at least 0.2 mol - (3) A compound represented by the following general formula [1] [wherein, RIVi is a nitro group, and R1 is a hydrogen atom. ~C, represents a lower alkyl group. M represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an ammonium ion. ] (2) Claim 1 characterized in that the silver halide photographic light-sensitive material contains a tetrazaindene compound.
Image forming method described in section. (3) The image forming method according to claim 1, wherein the silver halide photographic light-sensitive material contains a Group 8 metal salt. (4) The silver halide photographic light-sensitive material is 3 on the photosensitive layer side.
1Ar? The image forming method according to claim 1, wherein the image forming method has the following amount of gelatin. (5) The image forming method according to claim 1, wherein the developer contains an organic solvent. (6) The ratio (
(Na+)/(K'')). (7) The image forming method according to claim 1, wherein the developer contains a compound represented by the following general formula [...]. General formula (if) j〆”5・, [In the formula, 2 represents a heterocycle containing a nitrogen atom. M represents the same meaning as in the general formula [I].]