JPH0429233A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow development processing with a smaller amt. of replenishing liquid at the time of processing with an automatic developing machine by processing a photosensitive material with a water-soluble alkaline developer contg. at least one kind of specific compds. CONSTITUTION:The photosensitive material is processed with the water-soluble alkaline developer contg. at least one kind of the compds. expressed by formula I to formula IV. In the formulas I to IV, X denotes a hydrogen atom, hydroxy group, etc.; M<1>, M<2> denote a hydrogen atom, alkaline metal atom, etc.; B1, D1 denote and aliphat. group, alicyclic group, etc.; m1, n1 denote 1, 2 and 3 number; p denotes 1, 2; A2, E2 denote -CO-O-M, -SO2-O-M, etc. (M is univalent cation); R, R' denote a phenyl group, lower alkyl group; M denotes hydrogen, alkaline metal. The amt. of the development replenishing liquid of the automatic developing machine is decreased in this way.

Description

[Detailed Description of the Invention] (Background of the Invention) Black and white silver halide photographic light-sensitive materials generally undergo development and development after exposure.
It is processed through the steps of fixing, washing, and drying. Nowadays, most of them are processed using automatic processors (hereinafter abbreviated as automatic processors). At that time, the developing process is normally carried out while replenishing a certain amount of developer in proportion to the area of the photosensitive material. Conventionally, so-called sheet-shaped XH materials such as X-ray photography and Graphic Arts sensitive materials have been used.
2 to developer replenisher 22zomz or more, 3301 to %
It was common to supplement the above.

However, photographic developer waste has a high chemical oxygen demand (so-called C, 0.D) and biological oxygen demand (so-called B,
O,D))r! Therefore, developer waste liquid is subjected to chemical or biological treatment to render it harmless before it is disposed of. Since treatment of these waste liquids imposes a large economical burden, a development method that requires a small amount of development auxiliary liquid has been desired.

However, as the amount of developer replenisher decreases, the amount of silver that accumulates in the developer tank decreases to zero, and the so-called silver deposits on the walls, rollers, etc. of the automatic processor and is transferred to the surface of the silver halide photosensitive material to be processed. This results in a serious defect: dirt.

Furthermore, with the progress and development of the electronics field, speed is now required in all fields, and the field of silver halide photographic processing is no exception.

In particular, the need for rapid processing is increasing in the development processing of sheet-like photosensitive materials such as Graphic Arts photosensitive materials, X-ray photosensitive materials, photosensitive materials for scanners, and (LTT image recording photosensitive materials). .

Another advantage of rapid development processing is that the tank capacity required to develop a unit amount of photosensitive material per unit time is smaller, which means that an automatic developing machine can be smaller. big.

However, as the processing speed increases, problems such as a decrease in maximum density, sensitivity, and gradation tend to occur.

(Object of the Invention) Therefore, the object of the present invention is, firstly, to enable development processing using a small amount of replenisher per unit area when processing silver halide photosensitive materials in an automatic processor; An object of the present invention is to provide a method for rapidly developing a photosensitive material.

(Structure of the Invention) For the purpose of the present invention, the coating amount of gelatin is 2 on both sides of the support.
．． A silver halide photographic light-sensitive material having the following general formula (I), -format (n), -format (In) and having an average grain size of o, trtμ or less
It was also achieved by processing with an aqueous alkaline developer containing at least all seven compounds of type (IV).

In the formula, X represents a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxy group or a sulfo group. 811 and M2 may be the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group.

In the formula, Bl and DIU independently represent an aliphatic group, an alicyclic group, an araliphatic group, an aromatic group or a bicyclic J-membered ring or a 6-membered ring (which may be further fused to this ring). , 7 to 3 nitrogen atoms, 1 oxygen atom and 1 sulfur atom), ml and nl each contain l.
, λ and the number of 3, p and l and 2, and A2
and B2 are each independently of the formula % (in these formulas, is an alkyl group, Y may further be a phenylsulfonic acid group, a lower alkylsulfonyl group, or a phenylsulfonyl group, M is a heptavalent cation, and Z has the same meaning as X and Y, but a hydrogen atom is a group formed by U71r, where -CO-0-
When M is a group, the corresponding B1 and Dl mentioned above shall not have an α-amino group.

H ・・・・・・(■n R-CH-CH2-COOH [In the formula, RU represents a phenyl group or a lower alkyl group.

] B5-5o3 ・River...(■nR'-CH
・CH2・C0OH [In the formula, R/n phenyl group or lower alkyl group, M
represents hydrogen or alkali gold. ] Below, the general formula (I
), (It), (Ill) and (IV) will be explained in detail a.

- In format (1), X is a hydrogen atom, a hydroxy group,
lower alkyl groups (e.g. methyl, ethyl, propyl),
It represents a lower alkoxy group (for example, methoxy, nidoxin, a halogen atom (for example, chlorine, bromine), a carboxyne group or a sulfo group. Among these, a hydrogen atom is particularly preferred.

~11, M2 may be the same or different, and each represents a hydrogen atom or an alkali metal atom (eg, sodium, potassium) -! or an ammonium group.

Among the compounds represented by the general formula (n), preferred ones can be represented by the general formulas (If-/) and (II-2).

General formula (■-/ General formula (% formula%) In the general formula (It-/), R1 and R3 are hydrogen atoms, optionally substituted carbon atoms/-j alkyl groups, alkenyl groups, aralkyl groups, cyclo represents an alkyl group, an optionally substituted phenyl group, a j-membered or 6-membered heterocycle containing 7 to 3 nitrogen atoms, 7 oxygen atoms, or 1 sulfur atom, or a carboxylic acid group; Represents a direct bond or optionally substituted alkylene group, alkylidene group, phenylene group, aralkylene group or -CON HCH2-, A3 is -COOM or -803M (M is yl1 of general formula (1) , M2, and/or m2 is λ.

In the general formula (■-2), R4 and R5 represent a hydrogen atom or a methyl group. M is preferably a water cation or an alkali metal cation (for example, NaΦ or Honi■).

Of the compounds represented by the general formula (n-/), the general formula (n
−/a) is more preferred.

-Form (If-/a) 6 R7 In the general formula (n-/a), R6, R7i hydrogen atoms, optionally substituted alkyl groups (e.g. -CH3, -C2R5,
-CH20H1-CH2C0OH, etc.), cycloalkyl groups (e.g., methyl group, cyclohexyl group, etc.), phenyl groups that may be substituted (e.g., phenyl group, tolyl group, p-chlorophenyl group, p-7mi/phenyl group) j-membered and t-membered heterocycles containing 1 to 3 nitrogen atoms, or 7 oxygen atoms and 1 sulfur atom, such as p-sulfophenyl, p-sulfonamidophenyl, etc. , furyl group, thienyl group, etc.), or a carboxylic acid group, and R6 and R7 may be the same or different. l/, λ, 3 or ≠.

Next, in the general formulas (Ill) and (IV), the lower alkyl group represented by J R/ includes methyl, ethyl, propyl, etc., and the amino(lower)alkanethiosulfonic acid includes aminoethyl Thiosulfonic acid, etc.

Specific examples of the compound of general formula (1) are listed below.

(I-/ ■-2) (l-3 General formula ( A specific example of a chemical compound? Listed below.

(II-/] H3C-HC-8-8-CH-8CH3HOOC-H2
C CH2-COOH ■-2 HsuQC-H2C-8,8-CH2-(,:(JOH■
-Hiro3C HC -8-CH (F1a HOOC 0OH ■ f(3C-) (C-8-8 CH-CH3 82C-1-12C CH2-[82 a03S to 803a HOOC-HC-8-8-CH- COOHHOOC-H
2CCH2COOH (■-7 (II-r Thiolactic acid (■-ta) α-mercaptoisobutyric acid ■ / HOOC(CH2)2 5 S-(CH2)zCOOH (1-/2 HOOC(CH2)3-8-8- (CH2)3 C00
H■-73 CH3 CH3 HUOC-C-S-8-C-COOH CH3 CH3 (1-/ri CH3 CH3 0OC C-8-8-8-C-(,:(JOB H3 CH3 (1-/li CH3 CH3 HOOC-C-CH2-8-8-CH2-C-C(JO
HH3 CH3 (■-/ CH3 CH3 (■-/ HOOCCH2CH-8-8-(:HCH2-C0OH
6H5 6H5 (U-/r) 02NH2 802N) 12 (RO7 RIHOOC-C) l-CH2-8-8-CH2-CH-C
OOHHOOC-CH2CH2C00H (11-2/ CH3CH2 CH2CH3 (11-λkoHOOC-CH-CH-8-8-CH-CH-COOH
l-13 CH3 CH3 CH3 Low, 23) aUOC CH2 C) l-8-8-CHCH2-UUOHHOOC-CH
2 CH2C (JOH ■ +2 Hong ■ - Koyo) (1-21゜KOOC-CH2-NH-CO-CH-8-8-CH-
CO-NH-tI(2-COOKH3 CH3 (■-Kota■-37 (■-32 HOOC-CH2-8-8-8-(:H2-CUOH-
The formation fnJ of the compound (■) and (N) is listed below.

(■啼(■-λ (■-3 H CH3(,:HCH2-COOH (IV-/) 5O3K CH3-CHCH2-COOH General formula (1), (n), (III) or (
The amount of the compound represented by 8′) per liter of developer solution +
) o, /mmol to 10 mmol is preferred.

The composition of the halogenated substance of the black and white/halogenated button photosensitive dye used in the present invention includes silver chloride, silver bromide, chlorobromide,
Either silver iodobromide or silver iodochlorobromide may be used, but silver halide having a silver chloride content of 30% or more, particularly jOti or more, is preferable. The average grain size of the silver halide used in the present invention is not more than 00 μm. The silver halide photosensitive material used in the present invention preferably has an amount of 3,397 m or less.

The silver halide grains in the photographic emulsion used in the present invention have regular (
It may have a regular crystal structure, and particularly preferred are a cube and a tetradecahedron. Further, it may have an irregular crystal shape such as a spherical shape, a plate shape, a flat shape with an aspect ratio of 3 to 20, or a composite shape of these crystal shapes.

The interior and surface layers of the halogenated particles may be composed of a uniform phase or may be composed of different phases.

It may also be used in combination with a separately formed non-rogenized bride 41'.

:+The halogenated emulsion used in the invention contains cadmium salt, cadmium salt,
f#L salt, lead salt, thallium salt, ro/um salt or its complex salt, iridium salt or its complex salt? They may coexist.

The emulsion of the present invention may not be chemically sensitized (but may be chemically sensitized).
Known methods such as yellow sensitization, reduction sensitization, and gold sensitization can be used, and may be used alone or in combination. A preferred chemical sensitization method is sulfur sensitization.

As the sulfur sensitizer, in addition to the sulfur-poor compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanine, etc. can be used. Specific examples include US Pat. No. 574.91717, US Pat. ulo, 41
No. 9, same j, 721.661, same 3,30/, 3/
No. 3, same 3. It is described in No. tjt, Yjj. Preferred sulfur compounds include thiosulfate and thiourea compounds, and the pAg during chemical sensitization is preferably 7.3.
The following ranges are more preferable: 1-J7, J-ri, and O. Furthermore, Mo1sar, KIein Ge1at
ion,)'roc.

Symp, 2nd, 3ol-3ori (/970)
A method using a combination of polyvinylpyrrolidone and thiosulfate as reported by et al. also gives good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses gold compounds, mainly total complex salts. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium. Specific examples are US patents λ, μ≠r, o
It is written in To issue, English l special edition Otsu/1, Qbu issue 7, etc.

Examples of the primary sensitizers include metal salts, amines, formamidine sulfinic acid, and silane compounds, specific examples of which are listed in the US patent.

ur7,130, same 2. j/I, t91, same 2, Y
13. t09, 2.2r3. tio issue, 67≠,
It is described in No. 637.

In the silver halide emulsion in the light-sensitive material used in the present invention,
- It may be used alone or in combination of two or more types (for example, those with different average particle sizes, those with different halogen compositions, those with different crystal habits, and those with different chemical sensitization conditions).

Further, the silver halide emulsion layer may be a single layer or may be a multilayer (two layers, 3WI, etc.). In the case of multiple layers, different silver halide emulsions may be used,
The same one may be used.

4. Gelatin is advantageously used as the binder or protective colloid for the true emulsion, but other hydrophilic colloids can also be used. Examples include gelatin derivatives, graft polymers of gelatin and other polymers, and proteins such as albumin and casein.

Hydroxyethyl cellulose, carboxymethyl cellulose, cellulose conductors such as cellulose sulfate esters, sugar derivatives such as sodium alginate and starch conductors, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, For polymethacrylic, a multi-cylindrical synthetic hydrophilic compound such as polyacrylamide, polyvinylimidacil, polyvinylpyrazole, etc., either singly or as a combination thereof, can be used.

In addition to lime-treated gelatin, acid-treated gelatin may be used as the gelatin, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light, or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holophoranine dyes, styryl dyes, hemicyanine dyes, oquinol dyes, hemioquinol dyes, etc. can be used.

Useful sensitizing dyes for use in the present invention include, for example, RESEA.
RCHDISCLO8URE r tem / 7A
IIjlV-A term (/ri7 to year/ko month P,, 2J), same Item 1tjiX term (/ri7 to year P, ta3
7) or in the literature cited in .

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of each scanner light source can be advantageously selected.

For example, for A) argon laser light source, JP-A-60-1
No. 622117, Japanese Patent Publication No. 622117, JP-A-IAI'A! ! ,US%'
ffx, /Otsu/, No. 33/, West German patent 3t07
/ Non-plumerocyanines listed in issue.

B) Regarding the light source for helium-neon laser, see JP-A No. 3 O-A-≠25, JP-A No. 3/17λ, same! Trinuclear cyanine dyes shown in No. 022-T.

C) For LED light sources, thiacarbo described in Japanese Patent Publication No. 172/7, Japanese Patent Publication No. 172/7, Japanese Patent Publication No. 172/7, Japanese Patent Publication No. Cyanines.

D) JP-A-Sho for semiconductor laser light sources! Tarli 1
Tri-orbo/anines described in JP-A No. 03, JP-A-Sho tθ-rot-μ/, dicarbocyanines containing a Hiro-quinoline nucleus described in JP-A 7-Tak2≠K, etc. is advantageously selected.

The amounts of representative compounds of these sensitizing dyes are listed below.

A) Specific compound A-/) SO3H・N(C2H5)3 803H-N(C2H5)3 -j 0OH A-μ] 03K B) Specific compound B-/e -J 2H5 (-2H5C2H3 C) A specific compound of general formula (1) % formula % (wherein Y1 and Y2U each form a benzothiazole ring, benzoselenazole salt, naphthothiazole salt, nandoselenazole ring, or a heterocyclic ring such as a quinoline ring) These heterocycles represent a group of nonmetallic atoms necessary for
It may be substituted with an alkoxycarboxylic group or a halogen atom.

R1 and R2 each represent a lower alkyl group and an alkyl group having a sulfo group and a calhoquine group.

R3 represents a lower alkyl group. Xl represents an anion.

nl　　R2 represents 7 or 2.

n represents O and/or n= when it is an inner salt.

represents. ) In terms of medium, the canaloid compound C:2H5 2H5 D-≠ ■ ( 2H5 2H5 ■ ])-& Particularly preferred is the combination with the sensitizing dye of C), as it enables high sensitivity.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes may be used in combination for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may be included in the emulsion.

Research Disclosure (Res.
74 volumes/76
173 (issued February 2007), page 23, item 5.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing turnip IJi during the production process, presence or photographic processing of the light-sensitive material, or for the purpose of stabilizing the overall photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, promoinzimidazole, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro benzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; asaindenes, such as triasaindenes, tetraasaindenes (particularly couhydroquine-substituted (/).

3.3a, 7) Tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid; benzenesulfonic acid amide, etc.; many compounds known as anti-capri agents or stabilizers; Among these, preference is given to pencitrianols (e.g. j-methyl-benzotriazole) and nitroindazoles (e.g.!-
ditroindazole). Further, these compounds may be included in the entire treatment solution. Furthermore, JP-A-62-302
A compound that releases an inhibitor during development as described in No. 4t3 may be included as a stabilizer or for the purpose of preventing black spots.

The photographic light-sensitive material of the present invention may contain developing agents such as hydroquino/derivatives and phenidone derivatives for various purposes such as stabilizers and accelerators.

In the photographic photosensitive group V of the present invention, the four true emulsion layers and other hydrophilic colloid layers may contain no or all organic hardeners.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehyde stones (formaldehyde, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea 7x), dioxane derivatives, activated vinyl compounds (/
, 3. j-triacryloyl-hexahydro-5-triazine, /13-vinylsulfonyl-fluoropal/-), active halogen compounds (λ, ≠-dichloro-6~
hydroxy/-s-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), mucohalogen acids (mucochroic acid, etc.), which can be used in combination with MA. Other hydrophilic colloid layers include 6 fabric additives, antistatic, slippery improvement, emulsification dispersion, adhesion prevention, and photographic % improvement (PI, development acceleration, hardening, g increase) for various purposes. Various surfactant arrays may be included.

'IJ 'L +'i Sahonin (steroid form), Fulkire 7 oxide conductor (? lJ Eha polyethylene glycol, polyethylene glycol/polypropylene gel I
Jml condensates, polyethylene glycol alkyl ethers or dipolyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amide/amides, polyethylene oxide addition of licone Nonionic surfactants such as alkyl esters such as Grindol Mj4 (e.g. alkenylcono-phosphate polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols; alkyl carboxylates; Alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N
- Calhoki/groups, sulfo groups, phospho groups, sulfate ester groups, phosphate esters, such as alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxine ethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids or i 1J acid asters,
Ampholytic surfactants such as alkyl betaines and amine oxides; alkyl amine salts, aliphatic or aromatic ≠ primary ammonium salts, heterocyclic primary ammonium salts such as pyridinium and imidazolium, and aliphatic or hetero Cationic surfactants such as ring-containing phosphonium or sulfonium salts can be used.

In particular, the surfactant preferably used in the present invention has a molecular weight toot as described in Japanese Patent Publication No.
, 1 above.

Further, in order to prevent static electricity, it is preferable to use fluorine-based surfactants described in JP-A No. 6 O-ROT≠R.

The photographic light-sensitive material of the present invention contains a hydroquinone derivative (so-called DIR) which releases a development inhibitor in the photographic emulsion layer and other hydrophilic colloid layers in accordance with the density of the image during development.
-hydroquinone).

Specific examples include U.S. Pat. Otsuko No. 0,7176, U.S. Patent≠.

No. 377.4311, U.S. Patent No. 33, No. 7,
Tokukai Showa Ttar Kota,! No. 36, Tokukai Sho! ≠−67, ≠
/ri issue, Tokumen Akira! t-/33,331゜ issue, Tokukai Shoj &
-/13. j≠No. 2, Tokukai Akira! Tar No. 271,113,
3rd generation 5i' 01A3 j, 0≠
Examples include compounds described in No. 3z and No. 3110g.

The photographic light-sensitive material of the present invention may contain a matting agent such as hexachloride, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photosensitive material i#+ used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer containing alkyl (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, etc. as a single gold component can be used.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the invention preferably contain a compound having an acid group. Examples of compounds having acid groups include polymers or copolymers having organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid heptanomers such as acrylic acid, maleic acid, and phthalic acid as repeating units. Regarding these compounds, % Kaisho I, No. 223134, No. 67 Co. g μ 37, Otsu No. - No. J7, and No. T
The record in the specification of λ-Yo56≠No. 2 can be referred to. Among these compounds, ascorbic acid is particularly preferred as a low-molecular compound, and ascorbic acid is particularly preferred as a high-molecular compound, and as a high-molecular compound, a crosslinking compound having an acid monomer such as acrylic acid and two or more unsaturated groups such as divinylbenzene is preferred. It is a water-dispersible latex of a copolymer consisting of -.

The silver halide emulsion described above is coated onto a plastic film such as cellulose acetate film or polyethylene terephthalate film. Among these, polyethylene terephthalate film is preferably used.

The developing agent preferably used in the developer of the present invention is a dihydroquine benzene developing agent or an ascorbic acid developing agent. Dihydroquinobenzene type developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, imbrovir hydroquinone, methylhydroquinone, etc.

3-dichlorohydroquinone, 2. j-dichlorohydroquinone, λ, 3-diglomono A hydroquinone, λ,!
-Dimethylhydroquinone is available, but hydroquinone is particularly preferred. The developing agent is usually 0,0jmol/l-
It is preferably used in a concentration of 0.0, r mol/il.

In the present invention, especially in combination with the above-mentioned dihydroquine benzene-based developing drug or ascorbic acid developing agent, /-phenyl-3-
It is preferable to use pyrazolidones or p-aminophenols in combination.

/-phenyl-3-pyrazolidones include /-phenyl-j-hira:/l)ton, /-phenyl-+, +-
Dimethyl-3-pyrazolidone, /-phenyl-Hiro-methyl-≠-hydroquinemethyl-3-hirasoliton, /-phenyl-≠, 4L-dihydroxymethyl-3-pyrazolidone, /-phenyl-S-methyl-3-pyrazolidone,
/-p-aminophenyl-+, +-dimethyl-3-pyrazolidone, /-p-)lμmmethyl-3-pyrazolidone, and the like.

As p-amine phenols, HlN-methyl-p-aminephenol, N-(β-hydroquinethyl)-p-
Aminephenol, N-(4'-hydroxyphenyl)
Examples include glycine, no-methyl-p-amine phenol, and p-benzylaminophenol, among which N-methyl-p-amine phenol is preferred.

Dihydroxybenzene-based developing agent and /-phenyl-3-
When using a combination of pyrazolidones and 1ffp-aminophenols (the former at 00 Oj mol/l)
! ~O1j mol/l, the latter preferably used in amounts below 0.01 mol yiy.

Examples of sulfites include sodium sulfite, sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sulfite.

0.0 in sulfites. ．． It is preferably 20 mol/1 or more, particularly 0.30 mol/1 or more. Up to an upper limit rij , j mol/l, in particular 1. It is preferable to set the amount to λ mol/l.

The developer used in the invention may contain an amino compound to promote development. Especially the Tokkai Showa SL, -10t
2l goo, Tokukai Showa 6/-2t77! R de issue, special application 1-
A written amine compound can be used for Kota≠lr.

Depending on the pH value of the developer used in the present invention,! ~/ko, 3
The range is set to . As the alkaline agent used for setting the pH value, ordinary water-soluble inorganic alkali metal salts (eg, hydroxide, sodium carbonate) can be used.

In addition, the developer of the present invention uses a pH buffer agent such as boric acid, borax, tribasic sodium phosphate, and tribasic potassium phosphate, as well as a pH buffer agent as described in JP-A No. 60-23μ33. development inhibitors such as beautifying potassium and potassium iodide; organic solvents such as dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and methanol; indazole thread compounds such as j-nitroindazole,! - An antifoggant or a black pepper inhibitor such as a penztriazole compound such as methylbenztriazole; It is common to pre-dissolve the sulfite preservative-containing part and the separate part, and then mix the sulfite preservative-containing part with the painted part before use. moreover! - If the part in which ditroindazole is dissolved is completely alkaline, it will be colored yellow (it is convenient for handling, etc.).

Furthermore, a toning agent, a surfactant, a water softener, a hardening agent, etc. may be included as necessary.

As for the chelating agent in the developer used in the present invention, it is preferable that all the chelating agents having a chelate stability constant for ferric ions (Fe 2 ) of 3 + be greater than or equal to g.

Here, the chelate stability constant is L, G, Si l
1enA, EJjartel1 person, “5tabi l
i ty Con5tantsof 81etal
Complexes, The C
chemical Society, London (
/Riotsu4').

Written by S. Chaberek, A. E. Martell, @
Organic Sequestering Ag
ents.

It means a constant generally known by Willey (/Rijiri) and others.

In the present invention, examples of the chelating agent having a chelate stability constant of 2 or more for iron ions include carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds.

In the present invention, specific examples of compounds of the chelating agent having a chelate stability ratio of 2 or more with ferric ions include ethylenediamine diorthohydroxyphenylacetic acid,
Diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediamineniprobionic acid, iminonidiacetic acid, diethylenetriaminepentaacetic acid, hydroquinethyliminonidiacetic acid, /, 3-diaminobrono ξ Nol acetic acid, triethylenetetraminehexanoic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetracarboxylic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminebahetamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, /- Hydroquine ethylidene-l.

/-diphosphonic acid, /l/-diphosphonoethane-2=carboxylic acid, cophosphonobutane/, co.

≠-tricarboxylic acid, /-hydroxy=/-phosphonopropane-/, 2,3-tricarboxylic acid, catechol-3
，! -disulfonic acid, thorium triphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, and particularly preferred are, for example, diethylenetriaminepentachoic acid, triethylenetetraminehexaacetic acid, l,
3-diaminopropanoltetraacetic acid, glycol ether diamine full acid, hydroxyethylethylenediamine triM acid, cophosphonobutane/, 2,4'-tricarboxylic acid, /,/-diphosphonoethane-cocarboxylic acid, nitrilotrimethylene Phosphonic acid, ethylenediami/tetraphosphonic acid, diethylenetriami/pentaphosphonic lfi, /-hydroquinepropylidene/, /-
Examples include diphosphonic acid, /-amine ethylidene/, /-diphosphonic acid, /-hydroquinethylidene-/, /-diphosphonic acid, and salts thereof.

The usage amount of the above-mentioned KIRE-711 used in the present invention is 0.000. O/~toy, preferably 0.0
Good results are obtained in the range of 2 to λog.

The preferred pH of the developer is from ヂ,j to //,0. p
When the H value is lower than j, the development activity decreases rapidly, and p
H //, Of the overhang and the stability of the developer decreases.

In addition, a dialdehyde hardener or a bisulfite salt thereof may be impregnated with the developer of the present invention. Examples of these substances include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleic dialdehyde, succinic aldehyde, methoxysuccinic dialdehyde, methylsatannedialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxy/glutaraldehyde, α, α-dimethoxindialdehyde, β-imbrovir succinic dialdehyde, α, α-diethylsuccinic dialdehyde, butylmalein dialdehyde, or bisulfite adducts thereof and so on. It is used in grades V, unless the drying time is extremely long to the extent that the sensitivity of the photographic layer treated with the dialdehyde compound cannot be suppressed. Specifically, developer/l
7 to 50 g, preferably 3 to 10 I per serving. Among these, glutaraldehyde or its binitrous and mono-acid adducts are most commonly used.

Of course, if a bisulfite-adducted product of "dialdehyde-based dura" is used, the bisulfite of this adduct is also calculated as the sulfite in the developer.

In addition, "Photographic Processing Chemistry" by F.I. Mason, published by Focal Press (
Pages 22A-227 of JJ, 2013, US % Total 2nd. /ri3,0/! No., same No. ko.

Additives described in J9, 3T≠, JP-A-Sho≠, r-+lI-33, etc. may also be used.

In the present invention, the amount of developer replenisher is 20% per m2 of light-sensitive material.
It can be reduced to less than 0 m1, especially in the jog-so-tuty range.

The developer replenisher may have the same composition as the developer injected into the developing tank of the automatic processor at the beginning of development, or a solution with a different composition may be used.

The fixer used in the present invention is an aqueous solution containing thiosulfate, and has a pHJ of 1 or more, preferably 2 to 1! has.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is 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 about 3 mol/l.

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

In the fixing solution, tartaric acid, citric acid, gluconic acid, or derivatives thereof may be used alone or in combination. These compounds are the fixer/! Those containing o, oor moles or more are effective, especially 0.01 mole/! ~0.
0.3 mol/l is particularly effective.

The fixing solution may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid), pH adjusters (e.g. sulfuric acid), chelating agents with hard water softening ability, and special agents. The compound described in Japanese Patent Publication No. 1.2-7111/1998 can be included.

In the processing method according to the present invention, after the development and fixing steps, the film is treated with washing water or a stabilizing solution, and then dried.

Various types of automatic processors can be used in the present invention, such as a roller conveyance type and a belt conveyance type, but roller conveyance type automatic processors are preferred. Also, Tokukaihei/-
/AjO No. 0 and Japanese Patent Application No. 63-/♂631. By using an automatic processor with a developing tank with a small aperture ratio, there is less air oxidation and evaporation, and stable operation is possible in the processing environment. , the amount of replenishment can be further reduced.

A multistage countercurrent system (for example, two stages, three stages, etc.) has long been known as a method for reducing the amount of replenishment of washing water. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed by gradually contacting the processing solution in a clean direction, that is, the processing solution that is not contaminated with the fixing solution, resulting in even more efficient processing. Washing is done.

For the above-mentioned water-saving treatment or piping-free treatment, it is preferable to apply a protection measure to the washing water or stabilizing liquid.

As a means of preventing germs, there are the ultraviolet irradiation method described in Japanese Patent Application Publication No. 2003-120033, the method of using a magnetic field described in Japanese Patent Application Publication No. 2003-12003, and the method using a magnetic field described in No. 3/13 Method of purifying water using ion exchange resin described in JP-A-Sho t-ko//! /! ≠ issue, Mukai 62-/! The method using the antibacterial agent described in J-ri No. 52, Japanese Patent Application Sho J/-t30jθ, Mukai J/-t/J-ribu can be used.

Furthermore, L, F, West, “WaterQuali
ty Cr1teria Photo, Sci, &
Eng, Vol, 7 7%G(/ta j j), M, W.

Beach, “Microbiological
Growthsin Motion-pict
ure ProcessingSMPTE Jour
nal Vol, J'j, (/97t), R,0
, Deegan, @Photo Process
ingWash Water Biocides
”J, ImagingTech/0./#6t
(/rirg) and JP-A No. 7-rrti-λ, same J
7-j♂/≠3, same! g-10j/llj issue, same! 7
-/3λ/1+4, same! , r-/1tJ1, same j
7 Y 7 j No. 30, same! 7-/372! μ
Antibacterial axes, antifungal agents, surfactants, etc., which are described in the above issues, can also be used in combination.

Furthermore, in the water washing bath or stabilizing bath, R and T are used.

Kreiman, J., Image, Tech/
0゜(t) 211λ page (/rir≠) Inchiazoline compounds, Re5earch Disclos
ure Volume 20j, /1620!2 Otsu (/'PI/Yearj
22g≠! Inthiazoline compounds described in the Japanese Patent Application No. 7/1983 (Microbioci
It cannot be used together as de).

In addition, "Chemistry of antibacterial and antifungal" written by Hiroshi Hori, published by Sankyo Publishing (1982), "Handbook of antibacterial and antifungal technology" Japanese Society of Antibacterial and Antifungal, Hakuhodo (1987) When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank as described in Japanese Patent Application Laid-open No. Sho Jj-/13!0.

Further, it is also preferable to adopt a water washing process configuration as disclosed in Japanese Patent Application Laid-Open No. 1993-14-14TSRL/-TR.

Furthermore, in accordance with the process of the present invention, by replenishing the washing or stabilizing bath with protected water depending on the treatment, some or all of the overflow from the washing or stabilizing bath may be removed. -23! As described in No. 33, it can also be used in a processing liquid having a fixing ability, which is a processing step before that.

In the present invention, "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of an automatic processor until it is immersed in the next fixing solution. The time from immersion in the fixing tank solution until the next immersion in the washing tank solution (stabilizing solution), and the "washing time" refers to the time during which it is immersed in the washing tank solution.

In addition, the "drying time" is usually 3joC to 1
000C1 A drying zone is installed in which hot air of c-to°C is blown, and the period of time is defined as the time spent in the drying zone.

In the development process in the present invention, the development time is ! seconds to 3 minutes,
Preferably from g seconds to k minutes at the developing temperature/I'C-
600C power -4L<, 200C-1t00C is more preferable.

According to the present invention, the fusing temperature and time range from about /rc to about!
At OoC! Preferably seconds to 3 minutes,
6 seconds to 2 minutes is more preferable. Within this range, sufficient fixation can be achieved and the sensitizing dye can be completely eluted to the extent that residual color is desired.

O-
3 seconds to 3 minutes is preferable for ro'c, /! 0C～μOOC
″'c 6 seconds to λ minutes is more preferable.

According to the method of the present invention, the photographic material that has been developed, fixed, and washed (and stabilized) is dried by squeezing out the washing water, that is, passing through a squeeze roller. Drying is approximately ≠00
C to about 1000 C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 3 minutes, and particularly preferably about 5 seconds to 2 minutes ao-to-c.

According to the photosensitive material/processing system of the present invention, the total processing time f for development, fixing, washing, and drying can be reduced to 100 seconds or less, particularly 60 seconds or less. When performing such rapid processing, in order to prevent uneven development peculiar to rapid processing,
-/! It is possible to apply a roller made of rubber material to the roller at the outlet of the developer tank as described in /TAG No. 3 publication, or to apply a roller made of rubber material to the roller at the outlet of the developer tank as described in Japanese Patent Application Laid-open No. 4J-/J/R≠≠ publication. The discharge flow rate for stirring the developer in the tank should be set to 10 m/min or more, and furthermore, the
2t≠7! As described in the above publication, it is more preferable to make improvements such as stirring more strongly during standby at least during development processing. Furthermore, for rapid processing, it is more preferable that the rollers in the fixer tank are opposed rollers in order to increase the fixing speed.

By using opposed rollers, the number of rollers can be reduced and the processing tank can be made smaller.

In other words, it is possible to make the automatic processor more compact.

[Example J Hereinafter, the present invention will be explained in terms of examples, but the present invention is not limited thereto.

Example 1 Preparation of emulsion A/liquid 2 liquid 3 liquid 3! 'C, pH+, 2g in the l solution maintained at lC, and 3
While stirring the liquid, sharpen the blade for 70 minutes at the same time.
, itμn] were formed. Continue reading below≠liquid!
The liquid was added over a period of 70 minutes. In addition, potassium iodide 0. /! rifMJ particle formation was completed.

The liquid solution J was then washed with water by the flocculation method according to a conventional method, and gelatin 309f was prepared. pH! , /, pA
g7. ! Sodium thiosulfate g1n9 to gold chloride/2m? was chemically sensitized using 7JD ejjoc to obtain the optimum sensitivity, and as a stabilizer / , J , Ja
, 7-chitraasaindene λ001R9 was added. Finally, a silver iodochlorobromide cubic grain emulsion with an average grain size of 0.0 μm and containing 20 μm of silver chloride was obtained. (Variation coefficient %) Preparation of coating sample Add 3 infrared sensitizing dyes of the above sensitizing dyes 1)-3 to the above emulsion.
Infrared sensitization was carried out at 0.1 mol A g of 710 g.

Furthermore, for supersensitization and stabilization, ≠, q′bis=(
≠, t-dinaphthoxypyrimidin-2-ylamino)
- stilbene disulfonic acid disodium salt; 2. ! -dimethyl-3-allyrubenzothiazole iodo salt with silver 1
Each mole was 300m9, and the torn mouth was 300m9.

In addition, hydroquinone 700m97m and polyethyl acrylate latex with a gelatin binder ratio of -2j
%, and 2-bis(vinylsulfonylacetamido)ethane was added as a hardening agent at rt~/m2, and coated on a polyester support to give silver 3.0/m2 and gelatin/Og/m2.

0. Gelatin on top of this. ! 97m, as a matting agent polymethyl methacrylate with a particle size of Jμm/lO"9/m
A protective layer upper layer containing colloidal silica with El diameter/θ μm of 70 μm/m, dodenlebenzenesulfonic acid sodium salt as a coating aid, and a furan thread surfactant of the following structural formula ■, and gelatin O1 reference ■/ rn, polyethyl acrylate latex 22! m9/m,
10m97m2 and 20m2 of dyes with the following structural formula
■/m Dodecylbenzenesulfone y sodium salt as a coating aid? Added gl, yield increase lower layer all at the same time V'
All samples were prepared by applying C-coating.

(2) C8F'i 7so2N-CH2COOK (3H7) The support used in this example has a back layer and a back protective layer having the following composition.

[Back layer]

Gelatin /, 41g/m2 Sodium dotecylbenzenesulfonate dye ■ Dye ■ Dye ■ 7.3-Divinylsulfonyl monocoprobanol [Back protective layer] Gelatin polymethyl methacrylate (particle size ≠, 7 μm Sodium dotecylbenzenesulfonate fluorine System surfactant (■) Silicone oil to ■/rn 2 70 ■/rn 2 3!II#I; //m2 Om9/m2 60~/m2 s g /rn 2 30~/rn 2 2011297m2 .2 ■/m 2 100m9/m2 03K Temperature 1ttt'c when adding /liquid, 2nd, and 3 liquids to SO3 at the same time for 70 minutes while stirring to prepare emulsion B and prepare emulsion A.
The average grain size was 0.5mm using the same method as emulsion A except that the average grain size was 0. ≠
A cubic grain emulsion of silver iodochlorobromide with a particle diameter of 100 μm was obtained and designated as emulsion B (coefficient of variation: %). The coating sample was prepared using emulsion A.
We followed the example using .

Preparation of Emulsion C When preparing the coating sample, use Emulsion A except that the total amount of gelatin in the emulsion layer and the protective layer is J g /rn 2.
Emulsion C was prepared in the same manner as above.

The obtained sample was exposed to xenon flash light with an emission time of 10-6 seconds through an interference filter having a peak at 710 nm and a continuous wedge, and was used in an automatic processor FG710NH' manufactured by Fuji Yoshin Fiyam ■ to produce the following image. developer W,
X, Y% Z and fixer G manufactured by Fuji Photo Film ■
) t-F/', sensitometry was performed at the temperature and time shown below.

Furthermore, each developer was added at 1 tOv per film/m.
The entire treatment was carried out for 30 m while replenishing at a rate of i, and the soiling was also evaluated. In addition, the fixer Sodokokonoe was set at 300 general/m@current y! , 310C/j seconds Gradual Wash at 37°C for 2,7 seconds Water squeeze at 26°C Dry for λ, μ seconds jj 0c 1.3 seconds total
≠3. J second developer W Potassium sulfite t7.09 Hydroquinone 23・og≠-Methyl-
≠-hydroxymethyl-/-phenyl-3-virazolidone s, og potassium hydroxide //, 0g sodium carbonate (/hydrate) //, 0g potassium bromide
3.0jjj-methylbenztriazole 0.29 diethylene glycol j
Ji, Oji, hold water with a knife
pH 10, lj Developer solution
What I got.

Developer Y Addition of general formula (II-/7) to developer W/mM
/l Toguchi Eta Garo.

Developer solution Z Developer solution WE 7-phenyl-j, known as a silver stain inhibitor
-Mercaptotetrasol f/m M/l floating.

The reciprocal of the exposure amount giving attitude 3.0 was defined as the sensitivity and relative sensitivity. In addition, the slope of the straight line connecting the points of density 0.7 and 3°0 on the characteristic curve was set to all gradations. The silver stains after processing the 30m2 film were visually evaluated to grade J. did r4'J
Although silver stains occur on a very small portion of the ID film, it is at a level that is acceptable for practical use, but it is impractical if it is below "3". The blackening density of the fully exposed area is adjusted to the maximum density. The results obtained are shown in Table 1 below.

As shown in the results in Table 7, images with high gradations and high maximum density can be obtained with emulsion A consisting of a grain size of 02μ gelatin/97m2.

Furthermore, an uninvented processing method using a combination of a developer X or a developer Y containing a compound of 1-formation CI) and -formation (2) produces a high gradation, a high maximum density, and less silver staining. Furthermore, for comparison, in the case of developer Z containing /-phenyl-mercaptotetrazole, which is not a compound of the present invention, two-button stains were so bad that it could not be put to practical use with a yarn with a small amount of replenishment as in this example. level.

Claims (1)

[Claims] 1) The amount of gelatin applied is 2.0 g/m on both sides of the support.
A silver halide photographic light-sensitive material having a particle size of ^2 or less and an average grain size of silver halide of 0.4μ or less is expressed by the following general formula (I), general formula (II), general formula (III) or general formula A method for processing a silver halide photographic light-sensitive material, comprising processing with a water-soluble alkaline developer containing at least one compound represented by (IV). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) In the formula, X represents a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxy group, or a sulfo group. M^1 and M^2 may be the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the formula, B_1 and D_1 are each independently an aliphatic group, an alicyclic group, an araliphatic group, an aromatic group, or a heterocyclic group 5
membered ring or 6-membered ring (this ring may be further fused,
containing 1 to 3 nitrogen atoms and 1 oxygen atom or 1 sulfur atom), m_1 and n_1
are the numbers 1, 2 and 3, respectively, and p is 1 or 2
, A_2 and E_2 are each independently of the formula -CO-O-M, -SO_2-O-M, ▲ has a mathematical formula, chemical formula, table, etc. ▼, -S-Z and ▲ has a mathematical formula, chemical formula, table, etc. ▼ (In these formulas, X and Y are each a hydrogen atom or an alkyl group of up to 8 carbon atoms optionally substituted by a hydroxyl group, a carboxylic acid group, or a sulfonic acid group, and Y is further phenyl. It may be a sulfonic acid group, a lower alkylsulfonyl group or a phenylsulfonyl group, M is a monovalent cation, Z is X and Y
(has the same meaning as , except that it is not a hydrogen atom). However, when it is a group represented by -CO-OM, the corresponding B_1 and D_1 mentioned above do not have an α-amino group. ]▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [In the formula, R represents a phenyl group or a lower alkyl group. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) [In the formula, R' represents a phenyl group or a lower alkyl group, and M represents hydrogen or an alkali metal. ] 2) Add 2 developer solution per 1 m^2 of silver halide photographic light-sensitive material.
2. The processing method according to claim 1, wherein the processing is carried out using an automatic processor while supplementing at a ratio of 0.00 ml or less. 3) The processing method according to claim 1, using an automatic developing machine in which the total processing time of development, fixing, washing, and drying is 60 seconds or less.