JPH0695306A - Method for processing silver halide photographic sensitive material and processing agent - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material having buffer capacity and capable of being efficiently hardened. CONSTITUTION:This silver halide photographic sensitive material is processed in the presence of at least one kind of hydroxycarboxylic compd. with the hydroxyl group linked to all the alpha positions and with the sum total of the hydrogen atoms joined to the carbon atom at the alpha position controlled to 1. The fixer for the sensitive material contains at least one kind of the compd. or the granular processing agent for the sensitive material contains the processing agent as an aluminum compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a processing method and a processing agent for a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION A photographic processing agent, especially a fixing solution for printing plate making, contains a buffer agent for maintaining a constant pH. Usually, the pH of the fixer is
Is kept at 4.0-6.0 place. If the pH is too low, ammonium thiosulfate, which is a silver halide solvent, decomposes and sulfur precipitates and precipitates. If the pH is too high, aluminum hydroxide precipitates and precipitates. Therefore, it is necessary to keep the pH at about 4.0 to 6.0. Commonly used buffer agents include acetic acid, citric acid, tartaric acid and the like. Since these cause coordination with aluminum ions for hardening the gelatin film and cause hardening inhibition, it is necessary to add more aluminum ions than necessary.

[0003]

SUMMARY OF THE INVENTION With respect to the above problems, an object of the present invention is to provide a processing method and a processing agent for a silver halide photographic light-sensitive material having a buffering ability and capable of efficiently hardening a film. .

[0004]

The above object of the present invention is achieved by the following configurations.

1. A silver halide photographic light-sensitive material to be processed in the presence of at least one hydroxycarboxylic acid compound in which a hydroxyl group is bonded to all α-positions and the total number of hydrogen atoms bonded to carbon atoms in the α-position is 1 Processing method.

2. A fixing processing agent for a silver halide photographic light-sensitive material, containing at least one kind of the compound described in 1 above.

3. A granular processing agent for a silver halide photographic light-sensitive material, which is a processing agent satisfying the above item 2, and which is contained as an aluminum compound.

The present invention will be specifically described below.

Specific examples of the hydroxycarboxylic acid described in the claims are shown below, but the invention is not limited thereto.

[0010]

[Chemical 1]

The above compounds may be used alone or in combination of two or more. The total number of moles is
0.05 to 5.0 mol is preferable per 1 liter of liquid used, 0.07 to 1.0 m
ol is more preferred.

In the present invention, the hydroxycarboxylic acid may be contained anywhere in the photosensitive material, the developing solution and the fixing solution, and may be contained in the processing solution and the photosensitive material. Also,
It may be included in baths other than the developing, fixing and washing baths. Preferably, it is contained in the fixer.

Examples of the aluminum compound according to the present invention include aluminum acetate, aluminum ammonium sulfate, aluminum borate, aluminum bromide, aluminum chloride, aluminum cyclohexanebutyrate, aluminum ethylhexanoate, aluminum fluoride, aluminum hydroxide and aluminum iodide. , Aluminum lactate, aluminum laurate, aluminum nitrate, aluminum oleate, aluminum oxalate, aluminum sulfate and the like.

In the present invention, hydrates of the above compounds can be used. Preferred are aluminum sulfate, aluminum sulfate hydrate, and aluminum lactate.

<Granulation molding> As the granulation method, there are a compression molding method, an extrusion molding method, a stirring granulation method, a fluidized granulation method, and the like. It may be a relatively large tablet-like or brick-like lump,
Preferably, the granular shape is good, and more preferably, the particle size is 0.
It is a spherical granule of 1 mm to 3 mm. The surface of the granulated product may be coated with a substance such as a water-soluble polymer for the purpose of preventing oxidation or blocking (secondary aggregation of the granulated product). A binder may be used for granulation, if necessary.

As the binder, water or a commonly used granulating aid is preferably used, and a water-soluble or alkali- or acid-soluble polymer is used.

Specifically, for example, gelatin, pectin, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginic acid, gum chitanate. , Gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer,
Polyoxyethylene stearyl ether, polyoxyethylene ethyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, and other polyoxyethylene alkylphenol ethers, or the water-soluble properties described in Japanese Patent Application No. 2-203165. It is possible to use one kind selected from the binders or a combination of two or more kinds.

The amount of the binder is preferably up to 20 wt% of the granulated product, and if it exceeds this amount, it becomes a paste and adheres to the treatment agent container and is washed off with water, which makes it very difficult to use for work, which is a merit. It's gone. The preferable amount of binder is 1 to 10 wt%.

The photographic processing agent used in the present invention is not particularly limited, and any known photographic processing agent can be applied.

A specific developer contains the following developing agents. Examples of black and white developing agents include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate. Etc.), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl
-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl -
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone), aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) , 1-aryl-3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino -m-
(Methylphenyl) -3-aminopyrazoline, etc.) or a mixture thereof.

Further, as color developing agents, known primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline) , 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl
-N-β-hydroxyethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methanesulfonamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like).

[LFAMason Photographic Process]
ing Chemistry (Focal Press. 1966), 226-229
Pages, those described in JP-A-48-64933, etc. may be used.

These developing agents are usually used in an amount of 0.1 to 80 g / l, preferably 0.2 to 50 g / l.

The developer may further contain preservatives (eg, sulfurous acid, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine, etc.), alkaline agents (eg, hydroxide). , Carbonates, etc., solubilizers (eg polyethylene glycols, esters thereof, etc.), pH adjusters (eg organic acids such as citric acid), sensitizers (eg quaternary ammonium salts), development Accelerators, hardeners (such as dialdehydes such as glutaraldehyde), surfactants and the like can be included. The developer further includes an antifoggant (for example, a halide such as potassium bromide or sodium bromide, benzotriazole, benzothiazole, tetrazolethiazole, etc.), a chelating agent (for example, ethylenediaminetetraacetic acid, an alkali metal salt thereof, Polyphosphate, nitriloacetate, etc.) can be included.

The fixing treatment agent according to the present invention is preferably the following.

The fixing agent preferably contains thiosulfate. The thiosulfate is supplied as a solid, specifically, for example, as a lithium, potassium, sodium, ammonium salt or the like, and these are used after being dissolved. Among them, sodium and ammonium salts are preferably supplied and dissolved and used, and more preferably ammonium salts are supplied and dissolved and used, whereby a fixing solution having a high fixing speed can be obtained. The concentration of thiosulfate is preferably 0.1 to 5 mol / l, more preferable concentration is 0.5 to 2 mol / l, and further preferable concentration is 0.7 to 1.8 mol / l.

The fixing agent includes various acids, salts, chelating agents,
Additives such as surfactants, wetting agents and fixing accelerators can be included.

Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid and oxalic acid.

The silver halide emulsion used in the light-sensitive material may be one obtained by any of the acidic method, the neutral method and the ammonia method, and the grain size is preferably 0.2 μm or more and 0.5 μm or less.

The silver halide grains used in the emulsion are incorporated inside the grain and / or on the grain surface by adding a water-soluble rhodium salt and a water-soluble iridium salt in the process of forming the grain. The addition amount is 10 ^-6 per mol of silver halide.
~ ^10-9 mol is preferred.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer. May be particles mainly formed on the surface or particles mainly formed inside the particles.

The silver halide grains may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Pat.
3,756, 4,225,666, JP-A-55-26589, JP-B-55
-42737, etc., The Journal of Photographic Science (J.Photgr.Sci). By the method described in the literature such as 21.39 (1973), particles having a shape of octahedron, tetrahedron, dodecahedron, etc. can be prepared and used. Further, grains having twin planes may be used.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed.

Any grain size distribution may be used, an emulsion having a wide grain size distribution (referred to as polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as monodisperse emulsion). .) May be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the present invention, a monodisperse emulsion is preferred.
As the monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained within the grain size range of ± 20% centering on the average grain size r is 60% or more of the total weight of silver halide grains. Some are preferable, particularly preferably 70% or more, further preferably 80% or more.

The average particle diameter r Here, the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is maximum
Is defined. (3 significant digits, rounding down to the least significant digit 4) The grain size referred to here is the diameter of spherical silver halide grains, or the grain size of other than spherical grains.
It is the diameter when the projected image is converted into a circular image of the peripheral area.

The particle size can be obtained by, for example, photographing the particles with an electron microscope at a magnification of 10,000 times to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (measurement particles). The number is indiscriminately 1000 or more).

A particularly preferred highly monodisperse emulsion has a monodispersity degree of 20 or less, more preferably 15 or less, defined by (grain size standard deviation / mean grain size) × 100 = monodispersity degree. .

Here, the average particle size and the particle size standard deviation are obtained from ri defined above. Monodisperse emulsion is JP-A-54-4
It can be obtained by referring to 8521, 58-49938, 60-122935 and the like.

The light-sensitive silver halide emulsion can be used as it is without being chemically sensitized, that is, as a so-called unripened (Primitive) emulsion, but it is usually chemically sensitized. For chemical sensitization, Glafkides or Zelikman et al.,
Or edited by H. Frieser, Die Grundlagen der Photographischen Proz (Die Grundlagen der Photographischen Proz)
esse mit Silberhalo geniden Akademicche Verlagsges
The method described in ellschaft, 1968) can be used.

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitizing method using a reducing substance, gold or other noble metal compounds can be used. Examples of the sulfur sensitizer include thiosulfate,
Thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in US Pat.
1,574,944, 2,410,689, 2,278,947, 2,72
No. 8,668, No. 3,656,955, etc. As the reduction sensitizer, for example, primary tin salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds and the like can be used, and specific examples thereof are U.S. Pat.
No. 0, 2,419,947, 2,518,698, 2,983,609,
No. 2,983,610, No. 2,694,637, etc. For sensitizing precious metals, in addition to gold complex salts, platinum, iridium,
A complex salt of a Group VII metal of the periodic table such as palladium can be used, and specific examples thereof are U.S. Patents 2,399,083 and 2,448,0.
No. 60, British Patent 618,061 and the like.

The conditions such as pH, pH and temperature during the chemical sensitization are not particularly limited, but the pH value is 4 to 9, especially 5
-8 is preferable, and the pAg value is preferably kept at 5-11, especially 7-9. Also, the temperature is 40 to 90 ° C, especially
45 to 75 ° C is preferable.

In the photographic emulsion, in addition to the above-mentioned sulfur sensitization and gold / sulfur sensitization, a reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound can be used in combination.

As the photosensitive emulsion, the above emulsions may be used alone, or two or more kinds of emulsions may be mixed. In the implementation, after completion of the chemical sensitization as described above, for example, 4-
Hydmexi-6-methyl-1,3,3a, 7-tetrazaindene, 5-
Various stabilizers such as mercapto-1-phenyltetrazole and 2-mercaptobenzothiazole can be used.
If necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The emulsion may be free of unnecessary soluble salts after the growth of silver halide grains has been completed, or may be contained therein. The removal of the salts can be carried out according to the method described in Research Disclosure 17643.

Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salt,
Nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro groups or halogen atom-substituted compounds), heterocyclic mercapto compounds, such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyridines, the above heterocycle having a water-soluble group such as a carboxyl group and a sulfone group, mercapto compounds, thioketo compounds such as oxazoline thione, azaindenes such as tetraazaindenes Many compounds known as stabilizers can be added (especially 4-hydroxy substituted (1,3,3a, 7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acid and the like.

An example of a compound that can be used is the Theory of the Photographic Process, 3rd edition, by K. Mees.
1966) and the original documents are listed.

For more detailed specific examples of these and other uses, see, for example, US Pat. Nos. 3,954,474 and 3,9.
82,947, 4,021,248 or JP-B-52-28660.

Further, the silver halide photographic light-sensitive material has US Pat. No. 3,411,911, US Pat.
An alkyl acrylate-based latex described in, for example, No. 45-5331 can be included.

The silver halide photographic light-sensitive material may contain the following various additives. As a thickener or a plasticizer, for example, U.S. Pat.
904,604, JP-A-48-63715, Belgian patent 762,833
No. 3, U.S. Pat.No. 3,767,410, substances described in Belgian Patent 588,143, etc., such as styrene-sodium maleate copolymer, dextran sulphate, etc., as hardeners, aldehyde-based, epoxy-based, ethyleneimine-based, Active halogen-based, vinyl sulfone-based, isocyanate-based, sulfonate-based, carbodiimide-based, mucochloric acid-based, various hardeners such as acyloyl-based, as the ultraviolet absorber, for example, U.S. Patent 3,253,921, British Patent 1,3
Compounds described in each specification of No. 09,349, especially 2-
(2'-Hydroxy-5-t-butylphenyl) benzotriazole, 2- (2'hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3'-t -Butyl-5'-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl)
-5-chlorobenzotriazole etc. can be mentioned. Furthermore, coating aids, emulsifiers, penetrating agents for treating liquids, defoaming agents, and surfactants used for controlling various physical properties of light-sensitive materials include British Patent Nos. 548,532 and 1,216,389. No. 2,026,202
No. 3,514,293, Japanese Patent Publication No. 44-26580, No. 43-17922,
43-17926, 43-3166, 48-20785, French patent
202,588, Belgian patent 773,459, JP-A-48-10111
Although anionic, cationic, nonionic or amphoteric compounds described in No. 8 and the like can be used, among these, anionic surfactants having a sulfone group, for example, succinic acid ester sulfonates, Alkylbenzene sulfonates and the like are preferable. As an antistatic agent, Japanese Patent Publication No. 46-24159, Japanese Patent Publication No. 48-89979, and US Pat.
882,157, 2,972,535, JP-A-48-20785, 48-4
No. 3130, No. 48-90391, No. 46-24159, No. 46-39312
No. 48-43809, JP-A-47-33627 and the like.

In the manufacturing method, the pH of the coating solution is 5.3 to 7.
It is preferably in the range of 5. In the case of multi-layer coating, the coating liquid of each layer is mixed at the ratio of coating amount.
It is preferable that the pH is in the range of 5.3 to 7.5. pH is
If it is smaller than 5.3, the dura mater progresses slowly, which is not preferable and p
When H is larger than 7.5, it is not preferable that the photographic performance is adversely affected.

In the light-sensitive material, a slipping agent, for example, a higher aliphatic higher alcohol ester described in US Pat. Nos. 2,588,756 and 3,121,060, and US Pat.
Casein described in No. 9, high aliphatic calcium salt described in British Patent No. 1,263,722, silicon compounds described in British Patent No. 1,313,384, US Patent Nos. 3,042,522, 3,489,567 and the like may be included. Liquid paraffin dispersions and the like can also be used for this purpose.

Various additives can be further added to the light-sensitive material depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176 Item1764.
3 (December 1978) and Volume 187 Item 18716 (November 1979)
, And the relevant parts are summarized below.

Additive type RD17643 RD18716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer / supersensitizer 23 to 24 pages 648 right column to 649 right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers Pages 24 to 25 Page 649 Right column 6. Light absorbers, filter dyes 25 to 26 pages 649 Right column to 650 pages Left column UV absorbers 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binders page 26 same as above 11. Plasticizers / lubricants 27 pages 650 page right column 12. Coating aids / surfactants pages 26-27 same as above 13. Antistatic agents page 27 same as above The photographic processing of the silver halide photographic light-sensitive material is not particularly limited, and various methods can be used. The treatment temperature is usually chosen between 18 ° C and 50 ° C, but may be below 18 ° C or above 50 ° C.

[0056]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the embodiments of the present invention are not limited to these.

Example 1 <Adjustment of Fixing Agent> Ammonium thiosulfate 135.0 g Sodium sulfite 5.0 g Compound shown in Table 1 Boric acid 6.7 g Aluminum sulfate hydrate Amount shown in Table 1 The above additives were dissolved in water to 1 liter. Finish. The pH was 4.7.

<Swelling ratio> 12 printing sensitive materials RHG manufactured by Konica
It was cut into cm × 8 cm, printed out under a fluorescent lamp, and printed under the following conditions.

Developer 651K 28 ° C. 30 ″ Fixer (above) 28 ° C. 20 ″ Water wash 28 ° C. 30 ″ Each processing step uses a 1 l tank, and when moving to the next step,
Absorbed excess water with a hygroscopic paper. After washing with water and absorbing excess water, both sides of the film were quickly sandwiched with glass to prevent evaporation.

The swelling ratio was calculated using the following formula.

Swelling rate = 100 × water absorption per unit area (g)
/ Amount of gelatin per unit area (g) << Buffer capacity >> 50 ml of 651K to 500 ml of each fixing solution
The difference between the pH when added and the pH before addition was evaluated as the buffer capacity.

Example 2 <Preparation of Granules> A Ammonium thiosulfate 135.0 g Sodium sulfite 5.0 g B Sodium citrate hydrate 2.0 g Sodium oxalate 5.0 g Compound C shown in Table 2 C Boric acid 6.7 g Aluminum sulfate hydrate Amount shown in Table 2 The fixing agent constituent material is divided into the above A, B, and C parts, an appropriate amount of water in a weight ratio of 1 to 10% is added, and the mixture is agitated and mixed by an agitation granulator to obtain a diameter of about A cylindrical granule having a length of 1 mm and a length of about 2 mm was obtained. This granule was thoroughly dried at 200 ° C. and 20% RH to obtain a granulated product. These were dissolved in water to make 1 liter.
The pH was 4.7.

The results are shown in Tables 1 and 2 below.

[0064]

[Table 1]

As is clear from the results shown in Table 1 above, the treatment agent of the present invention has a hardening ability and a high buffering ability.

[0066]

[Table 2]

As is clear from the results in Table 2 above, even after the granulation and the dissolution, the treatment agent of the present invention has the film hardening ability and the high buffering ability.

[0068]

The processing method and the processing agent for a silver halide photographic light-sensitive material according to the present invention have a stuffing ability and can form a film efficiently.

Claims (3)

[Claims] 1. A hydroxyl group is bonded to all α-positions, and α-
A method for processing a silver halide photographic light-sensitive material, which comprises processing in the presence of at least one kind of a hydroxycarboxylic acid compound in which the total number of hydrogen atoms bonded to the carbon atom at the position is 1. 2. A fixing processing agent for a silver halide photographic light-sensitive material, comprising at least one kind of the compound according to claim 1. 3. A granular processing agent for a silver halide photographic light-sensitive material, which is a processing agent satisfying claim 2 and which is contained as an aluminum compound.