JPH06138604A - Agent and method for processing silver halide photographic sensitive material using same agent - Google Patents

Abstract

PURPOSE:To provide the tabletted agent for processing the silver halide photographic sensitive material improved in deterioration due to internal reaction in the tablets during the storage and hvgroscopicity, and enhanced in dissolution speed, and superior in processing stability and aptitude to a realistic environment, and to provide its processing method using this tabletted agent. CONSTITUTION:The tabletted agent for processing the photographic sensitive material is coated with a coating material containing at least one kind selected from a group of compounds F and a water-soluble polymer comprising as a structural component at least one of compounds represented by formula in which R1 is H or l-4C alkyl, and R1 is H or 1-3 C alkyl. The compounds F are as follows; glycols, glycerin esters, sucrose-fatty acid esters, a castor oil, organic esters, carbitols, cellosolves, and sorbitans.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material processing agent, and more specifically, it prevents skin sensitization troubles when handling a photographic processing agent, reduces packaging materials, particularly waste plastics, and further forms tablets. The present invention relates to a state-like photographic processing agent capable of improving storage stability of a processing agent, in particular, deterioration of a tablet due to an internal reaction in the tablet, and stable processing performance, and a processing method using the same.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials are usually developed using processing solutions such as black-and-white developing solution, fixing solution, reversal solution, adjusting solution, color developing solution, bleaching solution, bleach-fixing solution and stabilizing solution. Done and an image is obtained. Each processing solution used here is
It is supplied to the user as a treating agent kit in a container such as a plastic bottle in the form of one or more concentrated liquids or working liquids for ease of use. The user uses these treating agent kits as they are or by diluting and dissolving them with water to prepare a use liquid (starting liquid or replenishing liquid).

In recent years, in the photographic processing industry, the number of small-scale developing laboratories has been rapidly increasing by using a small automatic developing machine called a minilab. With the progress of minilabization, the amount of plastic bottles for processing agents and the like used also. , It is increasing rapidly year by year.

Because of its light and strong properties, this plastic has been widely used in addition to bottles for photographic processing agents. The worldwide production of plastics has been increasing year by year, and in 1988, it had grown to over 100 million tons per year. On the other hand, the amount of discarded plastic is enormous, and even in Japan, the production volume is about 40%.
% Is discarded year by year. When such waste plastic is dumped into the ocean, it causes deterioration of the habitat of marine organisms, and in Europe, because it is burned in an incinerator that lacks exhaust gas treatment equipment, acid rain, etc. It is also causing problems.

For this reason, there is an urgent need to implement countermeasures, and in Europe and the United States, legal regulations such as plastic recycling and use prohibition, or obligatory use of degradable plastics are becoming more active. It is the actual situation.

Under such circumstances, it is extremely unfavorable to use a large amount of plastic bottles as a processing agent for photographic use, although it is a part.

Therefore, it is conceivable that the concentrated liquid of the photographic processing agent is made into a powder, but in that case, there is a high possibility that fine powder may fly up and be inhaled by an operator at the time of dissolution, which may cause a health problem. However, there is a problem in that the processing agent components that have risen or flown up are mixed into another photographic processing solution, which causes contamination and causes trouble. Therefore, a technique of granulating a photographic processing agent to form a granular mixture, for example, has been proposed in JP-A Nos. 2-109042 and 2-109043, U.S. Patents 2,843,484 and 3-39735, Occupational health and safety problems due to scattered chemical dust, contamination of various processing liquids as impurities, or a casing phenomenon in which sedimentation / condensation occurs at the bottom of the container when dissolved, coating of powder with its own wet film causes poor dissolution, etc. In fact, the range of drugs suitable for powdering and granulating is extremely limited, which brings about problems such as hindrance to the mixing workability due to the above.

Therefore, tableting is a preferable form of the treating agent which takes advantage of the advantages of these dry conditions.
It has been proposed in the issue. However, it has been found that the storability of a color developing solution tablet or a fixing solution tablet is deteriorated when there is a material having a high hygroscopic property and is left naked. For this improvement, a method of separately granulating and tableting is DE3830023.
Etc.

However, it has been found that under high temperature and high humidity conditions, such as in the tropics, there is still insufficient moisture resistance. Also, in the case of tablets for color development, internal reaction in the tablet may become a problem such that the color developing agent and alkali react with each other to disintegrate the tablet, and in the case of tablets for fixer, the fixing component is transformed into a sparingly soluble compound. I understand.

On the other hand, in the case of pharmaceuticals and the like, further coating of tablets is disclosed in, for example, Japanese Patent Publication No. Sho 46-22955. Further, JP-A-59-121040 discloses a technique for microencapsulating a photographic processing agent. However, these tablets have a slow dissolution speed and are not suitable for continuous processing in a developing machine. Further, when applied to a photographic processed tablet, there is a problem that the internal reaction in the tablet is large and the long-term storage resistance is poor.

[0011]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to improve the internal reaction in the tablet during the storage of the processing agent for tablet silver halide photographic light-sensitive material and the resulting deterioration of the tablet, the improvement of hygroscopicity, and the dissolution speed. To provide a tablet-like processing agent for a silver halide photographic light-sensitive material which is excellent in processing stability and is excellent in social stability and a processing method using the processing agent.

[0012]

The above object of the present invention is covered with a coating material containing at least a water-soluble polymer containing at least a compound represented by formula (I) as a constituent component and at least one selected from the compound group F. It has been found that the present invention can be achieved by a processing agent for tablet-shaped silver halide photographic light-sensitive material characterized by the above.

[0013]

[Chemical 2]

[In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Compound Group F Glycols Glycerin Esters Sucrose Fatty Acid Esters Castor Oil Organic Acid Esters Carbitols Cersolves Sorbitans The present invention will be described in more detail below.

In the present invention, a tablet is a powder or granule of a photographic processing composition which is compressed into a plate-like or lump-like shape (for example, lens shape, sphere, triangle, quadrangle, cylinder or cylinder). A chemical agent that dissolves or dissolves in dissolved water or a processing solution to release the photographic processing composition. For example, the photographic processing agent composition may be mixed with an excipient or a binder to form a powder, which may be shaped into a tablet having a certain size and hardness with a compression tablet machine, which has the advantage of accurate dose. . It should be noted that the size may be appropriately determined according to the mode of use.

[0016]

[Detailed Description of the Invention] The technology of packaging and protecting using a water-soluble polymer has been applied to the packaging of agricultural chemicals, water treatment agents, detergents, bactericides, etc., for example, Japanese Patent Application No. 2-1559.
99, JP-A-62-4800, 63-12466 and 61-57700
No. specification etc. However, there is no known application example to a photographic processing agent which is directly coated with a water-soluble polymer instead of packaging with the water-soluble polymer as described above, and is further selected from the water-soluble polymer and the above compound group F. It was quite surprising that the effects of the present invention as described above can be obtained by applying the compound to a photographic processing agent.

The water-soluble polymer of the present invention is a water-soluble polymer containing at least the compound represented by the general formula (I) as a constituent component.

[0018]

[Chemical 3]

R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Examples of compounds (monomers) represented by the general formula (I) of the present invention will be given.

[0021]

[Chemical 4]

The water-soluble polymer of the present invention can be obtained by a known polymerization method. For example, a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. can be mentioned.

The water-soluble polymer of the present invention comprises the compound represented by the general formula (I) as a constituent component. Preferably 5
Copolymerization is carried out at 100 mol%, more preferably 10 to 90 mol%.

In the present invention, as the monomer copolymerizable with the compound represented by the general formula (I), acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamide, acrylic acid ester, methacrylic acid ester, styrene, styrene can be used. Examples thereof include derivatives, olefins, vinyl acetate, and trimethylammonium ethyl methacrylate.

The average weight molecular weight of the polymer of the present invention is 1,
It is 000 to 1,000,000, preferably 3,000 to 500,000, particularly preferably 10,000 to 100,000.

Examples of preferred polymers of the present invention are given.

[0027]

[Chemical 5]

, Are preferred as color developing tablet-like processing agents and fixing tablet-like processing agents.

, Is preferred for the bleaching tablet processing agent and the bleach-fixing tablet processing agent.

These are Eudragit L30D-55, L100-55, L100, S100, RS100L, RSP manufactured by Rohm Pharma.
OL, RS30DL, RS100, RSPO, RS30D, N
It is also possible to purchase it as E30D.

The compounds of the present invention will be described in detail. More preferable compounds of the compound group F include polyethylene glycol, triacetin, glycerin fatty acid ester, sucrose fatty acid ester, castor oil, polyoxyethylene sorbitan ester (commercial product Tween), triethyl citrate, dibutyl phthalate, diisopropyl succinate, etc. Examples of the organic acid esters include carbitols such as carbitol, butyl carbitol acetate, and dibutyl carbitol; cellosolves such as ethyl cellosolve and phenyl cello rib; ethylene glycol and propylene glycol.

Illustrative compounds are shown below, but the invention is not limited thereto.

Exemplified Compounds (1) Polyethylene glycol (2) Triacetin (3) Polyoxyethylene sorbitan monolaurate (Tween 20) (4) Poly (ethylene sorbitan) monopalmitate (Tween 40) (5) Poly (ethylene sorbitan) mono Stearate (Tween 60) (6) Polyoxyethylene sorbitan monooleate (Tween 80) (7) Triethyl citrate (8) Dibutyl phthalate (9) Diisopropyl succinate (10) Carbitol (11) Butyl carbitol acetate ( 12) dibutyl carbitol (13) ethyl cellosolve (14) phenyl cellosolve (15) ethylene glycol (16) propylene glycol Of these, (1),
(2), (3), (7), and (16). The polyethylene glycol of (1) has an average molecular weight of
It is preferably 200 or more and 1000 or less.

The addition amount of these plasticizers is preferably 0.01 to 50%, particularly preferably 0.1 to 30%, based on the weight of the coating agent.

Next, the tablet according to the present invention will be described.
The tablet referred to in the present invention means one obtained by compressing and forming powder into a certain shape, or one obtained by once granulating and then forming into a certain shape by compression.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is preliminarily formed on the surface of the photographic processing agent. Any means such as forming a coating layer by spraying can be adopted (Japanese Patent Application No. 2-135887, No. 2-203165,
2-203166, 2-203167, 2-203168, 2-304
See No. 09).

A preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed. There is an advantage that solubility and storability are improved as compared with a solid processing agent formed by a tableting process by simply mixing solid processing agent components, and as a result, photographic performance becomes stable.

The granulation method for tablet formation includes rolling granulation,
Known methods such as extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation can be used. The average particle size of the obtained granulated product is preferably 100 to 800 μm, and more preferably 200 to 750 μm. Average particle size smaller than 100 μm or 80
When it is larger than 0 μm, when the above granules are mixed and compressed under pressure, the components become non-uniform, so-called segregation is not preferable.

Further, the particle size distribution is preferably such that 60% or more of the granulated particles are within a deviation of ± 100 to 150 μm.

When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine or a briquetting machine may be used. it can. The solid processing agent obtained by compression under pressure can have any shape, but a cylindrical type, so-called tablet is preferable from the viewpoint of productivity and handleability.

More preferably, at the time of granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a bleaching agent and a preservative.

A method for producing a tablet treating agent is described in, for example, JP-A-51.
-61837, 54-155038, 52-88025, British Patents 1,2
It can be produced by a general method described in the specification of 13,808 and the like, and the granule treating agent is, for example, JP-A-2-09042,
It can be produced by a general method described in the specifications such as 109043, 3-39735 and 3-39739. Furthermore, the powder processing agent is, for example, JP-A-54-133332, British Patent 725,892,
It can be produced by a general method as described in the specifications such as German Patent No. 729,862 and German Patent No. 3,733,861.

The bulk density of the tablet of the present invention is preferably 1.0 to 2.5 g / cm ³ from the viewpoint of the effect of the present invention. This is because if it is less than 1.0 g / cm ³ , the strength is weak, and if it exceeds 2.5 g / cm ³ , the solubility is low.

The maximum diameter of the tablet of the present invention is preferably 10 to 40 mm. When it is less than 10 mm, not only is the specific surface area large and it is disadvantageous in moisture proofing, but also for photoprocessing applications, the working efficiency decreases, such as the frequency of loading of tablets increases. If it is larger than 40 mm, the polymer coating tends to be non-uniform, which is inconvenient to handle.

The shape of the tablet of the present invention is, in order to coat the polymer uniformly, rather than the usual disc shape,
It is preferable that the upper and lower surfaces are curved surfaces having a constant curvature. Furthermore, it is more preferable that the tablet has a so-called double radius shape having two curved surfaces having a smaller radius of curvature closer to the edge portion of the tablet.

In the tablet-type photographic processing agent of the present invention, all the components of one tablet may be uniformly mixed and tableted, or the constituent components may be layered and tableted. Furthermore, the inside and the outside of the tablet may be formed into different tablets.

The tablet-type photographic processing agent of the present invention may be tableted after being subjected to commonly used pretreatments such as granulation before mixing, mixing with an adhesive or coating with a coating agent. Good.

Next, a method for coating the polymer with tablets will be described. First, a coating solution is prepared by dissolving or suspending a polymer in water, an organic solvent or a mixture of both. Examples of the solvent for the coating liquid preferably used in the present invention include water, methanol and ethanol, and a mixture thereof is also preferable. As a coating method, coating with a pan, coating with a fluidized bed apparatus, a method of immersing a tablet in a coating liquid, or the like can be used, but coating with a pan is preferable. The method of coating with a pan is to pour or spray the coating liquid onto the fluid surface of the tablet while rotating the pan containing the tablet,
The operation of sending hot air into the pan to remove the solvent and dry it is continued until a predetermined coating amount is reached. At this time, the pressure in the pan may be reduced. Further, two or more kinds of coating agents may be sequentially changed and sprayed to form a multi-layer coating.

The polymer of the present invention is preferably coated in an amount of 0.1 to 30% based on the weight of the tablet processing agent to be coated. If it is less than 0.1%, the moisture-proof effect is small, and if it exceeds 30%, the solubility is poor and the effect on photographic performance is large. Furthermore, a coverage of 0.5 to 15% is particularly preferred.

Examples of the silver halide color photographic light-sensitive material processing agent of the present invention include a color developing agent, a bleach-fixing agent, a fixing agent, a rinsing agent, a stabilizing agent, a first developing agent, a reversing agent, and an adjusting agent. . Carbonate, bicarbonate, thiosulfate,
When at least one kind of thiocyanate is contained, the effect of the present invention is more remarkably exhibited.

When the photographic processing agent in the present invention is a color developing agent, as the color developing agent used, a p-phenylenediamine compound having a water-soluble group exerts the desired effect of the present invention, and fog It is preferably used because it rarely occurs.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine, and With respect to the skin, not only has the advantage that the skin is less susceptible to rash, but the object of the present invention can be achieved more effectively by using the color developing agent of the present invention.

Examples of the water-soluble group include those having at least one amino group of the p-phenylenediamine compound or on the benzene nucleus. Specific water-soluble groups include-(C
_{H 2) nCH 2 OH, -} (CH 2) mNHSO 2 (CH 2) nCH 3, - (CH 2) mO (CH 2) n
_{CH 3, - (CH 2 CH} 2 O) nCmH 2 m +1 (m and n each represents an integer of 0 or more.), - COOH group, and as -SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-203169, 26 to 31.
(C-1) to (C-16), 4-amino described on page
-3-Methyl-N- (3-hydroxypropyl) aniline and the like can be mentioned.

The color developing agent is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone or 4-hydroxymethyl-4-methyl-1-phenyl-3.
-It may be used in combination with pyrazolidone or metol.

Further, in the present invention, not only the effects of the present invention are exerted when the color developer according to the present invention contains the compounds represented by the following general formulas [A] and [B]. This is also one of the preferred embodiments because it produces the effect of less fog occurring in the unexposed portion.

[0058]

[Chemical 6]

In the formula, R ₁ and R ₂ each represent an alkyl group, an aryl group, an R ₃ CO— group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. or,
R ₁ and R ₂ may form a ring.

In the general formula [A], the alkyl groups represented by R ₁ and R ₂ may be the same or different and each is preferably an alkyl group having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxyl group, a phosphoric acid group, a sulfo group or a hydroxyl group. R ₃ represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and aryl group of R ₁ , R ₂ and R ₃ include those having a substituent, and the ring which may be formed by R ₁ and R ₂ is a hetero ring such as piperidine, pyridine, triazine or morpholine. A ring is included.

[0061]

[Chemical 7]

In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R ₁₄ represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted group. It represents an unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group or amino group. The heterocyclic group is a 5- or 6-membered ring, is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R ₁₅ is -CO-, -SO
It represents a divalent group selected from 2- or -C (= NH)-, and n is 0 or 1. Particularly when n = 0, R ₁₄ is an alkyl group,
Represents a group selected from an aryl group and a heterocyclic group, R ₁₃ and R
₁₄ may together form a heterocycle.

Specific examples of the hydroxylamine compound represented by the general formula [A] are shown in US Pat.
3,293,034 and 3,287,124, etc.,
Particularly preferred specific exemplified compounds include Japanese Patent Application No. 2-2031
(A-1) to (A-39) described on page 36 to 38 of the specification of 69 and (1) to (5) described on page 3 to 6 of the specification of JP-A-3-33845.
3) and (1) described in JP-A-3-63646, pages 5-7.
~ (52).

Specific examples of the compound represented by the above general formula [B] include (B-1) to (B-33) described in Japanese Patent Application No. 2-203169, pp. 40 to 43, and JP-A Nos. (33), No. 3-33846, (1) to (56) described on pages 4 to 6.

The compounds represented by the general formula [A] or the general formula [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluenesulfonic acid group, oxalate, phosphate, acetate and the like.

Further, a hydroxylamine compound represented by the following general formula [A '] is also preferably used as a preservative for the color developing solution.

[0067]

[Chemical 8]

In the formula, L represents an alkylene group which may be substituted, A is a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonia group and a carbamoyl group, respectively. Alternatively, it represents a sulfamoyl group, and R represents a hydrogen atom or an optionally substituted alkyl group.

Specific examples of the compound represented by the general formula [A '] include (1) to (54) described in JP-A-3-84044, page 4, lower left column to page 6, lower right column. But above all (1)
And the following compounds represented by (7) are preferable.

(1) HON (CH ₂ CH ₂ COOH) ₂ (7) HON (CH ₂ CH ₂ SO ₃ H) _{2 The} compound represented by the general formula [A ′] is an alkyl compound obtained by alkylating a commercially available hydroxylamine compound. It is obtained by a chemical reaction. For example, West German Patent 1,159,634 and Inorganica Chimica Acta., 93
(1984) 101 to 108 and the like according to the synthesis method.

A small amount of sulfite can be used as a preservative in the color developer and the black and white developer according to the present invention. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like.

It is necessary to use a pH buffering agent in the color developing agent and the black and white developing agent according to the present invention, and as the pH buffering agent, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and triphosphate are used. Sodium, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), Potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2-
Examples thereof include potassium hydroxybenzoate (potassium 5-sulfosalicylate) and the like.

As the development accelerator, Japanese Examined Patent Publication No. 37-16088,
37-5987, 38-7826, 44-12380, 45-9019
And the thioether compounds represented by U.S. Pat. No. 3,813,247, p-phenylenediamine compounds represented by JP-A-52-49829 and 50-15554, and JP-A-50-137726.
JP-B-44-30074, JP-A-56-156826 and 52-43
Quaternary ammonium salts represented by 429, US Pat.
P-aminophenols described in 10,122 and 4,119,462, U.S. Patents 2,494,903, 3,128,182 and 4,230,79
No. 6, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,48
Amine compounds described in 2,546, 2,596,926 and 3,582,346, etc., Japanese Patent Publication Nos. 37-16088, 42-25201, U.S. Patents 3,128,183, 41-11431, 42-23883 and U.S. If necessary, polyalkylene oxide represented by Patent 3,532,501 and the like, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added.

Chloride ions and bromine for the purpose of preventing fog, etc.
Ions may be used in the color developer. In the present invention
At 1.0 x 10^-2~ 1.5
× 10 ^-1Mol / liter, more preferably 3.5 × 10^-22 to
1 x 10^-1Contains mol / liter. Chloride concentration is 1.
5 x 10^-1If it is more than mol / liter, development will be delayed and quick
It is not preferable to obtain a very high maximum concentration. Also, 1.0 × 1
0^-2, Especially 3.5 × 10^-2Below mol / l, stain
Occurs, and furthermore, fluctuations in photographic properties (especially minimum
(Concentration) becomes large, which is not preferable.

In the present invention, the color developer preferably contains 3.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / liter of bromine ions. More preferably 5.0 × 10 ^{-5 to} 5 × 10 ^-4 mol /
It is a liter. Particularly preferably, it is 1 × 10 ^{−4 to} 3 × 10 ⁻⁴ mol / liter. Bromine ion concentration is 1 × 10 ^-3 mol /
When the amount is more than liter, the development is delayed, the maximum density and the sensitivity are decreased, and when it is less than 3.0 × 10 ^-5 mol / liter, stain is generated, and the photographic property variation (especially the minimum density) is generated during continuous processing. Is not preferable.

When added directly to the color developer, sodium chloride, potassium chloride, chlorine chloride,
Ammonium chloride, nickel chloride, magnesium chloride,
Examples thereof include manganese chloride, calcium chloride, and cadmium chloride, with sodium chloride and potassium chloride being preferred.

Further, it may be supplied in the form of a salt against the color developing agent and the optical brightening agent added to the developing agent.

As a bromide ion supplying substance, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, Thallium bromide may be mentioned, of which potassium bromide and sodium bromide are preferred.

In addition to chlorine ions and bromine ions, an optional antifoggant can be added to the color developing agent and the developer of the present invention. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

From the standpoint of the effect of the present invention, it is preferable that the color developing agent and the developing agent of the present invention contain a triazinyl stilbene type optical brightening agent. As the fluorescent whitening agent, compounds represented by the following general formula [E] are preferable.

[0081]

[Chemical 9]

In the above formula, X ₂ , X ₃ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine,
Alkyl group, aryl _{group, -N (R 21) (R} 22) group,

[0083]

[Chemical 10]

Or represents --OR ₂₅ . Where R ₂₁ and R
₂₂ is a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), R ₂₃ and R ₂₄ are an alkylene group (including a substituent), and R ₂₅ is a hydrogen atom or an alkyl group. (Including a substituent) or an aryl group (including a substituent), and M represents a cation.

The details of each group of the general formula [E] or the substituents thereof are the same as those described in Japanese Patent Application No. 2-240400, page 62 to line 8 to page 64 to line 3 from below. As specific compounds, E-1 to E-45 described on pages 65 to 67 of the same item can be mentioned.

The above compound can be synthesized by a known method. Representative compounds are exemplified below, and among them, particularly preferably used are E-4, E-24, E-34,
E-35, E-36, E-37 and E-41. The amount of these compounds added is preferably in the range of 0.2 to 10 g, and more preferably 0.4 to 5 g, per 1000 ml of color developing solution.

[0087]

[Chemical 11]

[0088]

[Chemical 12]

Further, in the color developing agent and the black and white developing agent used in the present invention, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. The compounds described in No. 9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include, for example,
N-methyl-p-aminophenol hexaulfate (methol), phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride, etc. It is known and the addition amount is usually preferably 0.01 to 1.0 g / l.

Furthermore, various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

Further, for the color developing agent and the black and white developing agent, a chelating agent represented by the following general formula [K] described in Japanese Patent Application No. 2-240400, page 69, bottom, line 9 to page 74, and its examples are given. Compound K
Addition of -1 to K-22 is preferable from the viewpoint of effectively achieving the object of the present invention.

[0093]

[Chemical 13]

Among these chelating agents, K
-2, K-9, K-12, K-13, K-17, K-19 are preferably used, and particularly, the effect of the present invention when K-2 and K-9 are added to the color developing agent. Plays well.

The amount of these chelating agents added is preferably 0.1 to 20 g, and more preferably 0.2 to 8 g, per liter of the color developing agent and the black and white developing agent.

Further, the color developing agent and the black and white developing agent can contain anionic, cationic, amphoteric and nonionic surfactants.

If necessary, an alkyl sulfonic acid,
You may add various surfactants, such as an aryl sulfonic acid, an aliphatic carboxylic acid, and an aromatic carboxylic acid.

When the processing agent according to the present invention is a bleaching agent or a bleach-fixing agent, the bleaching main agent preferably used is an organic acid represented by the following general formula [L], [M], [N] or [P] It is a ferric complex salt.

[0099]

[Chemical 14]

In the formula, A _{1 to} A ₄ may be the same or different and each represents --CH ₂ OH, --COOM or --PO ₃ M ₁ M ₂ . M, M
₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

The compound represented by the general formula [L] will be described in detail below.

[0102] Incidentally, the group A ₁ to A ₄ represents the detailed description is omitted because it is A ₁ to A ₄ of the first line 15 to page 15, line 3 according page 12, Japanese Patent Application No. 1-260628 .

Preferred specific examples of the compound represented by the above general formula [L] are shown below.

(L-1) 1,3-Propanediaminetetraacetic acid (L-2) 2-Hydroxy-1,3-propanediaminetetraacetic acid (L-3) 2,3-Propanediaminetetraacetic acid (L-4) ) 1,4-Butanediaminetetraacetic acid (L-5) 2-Methyl-1,3-propanediaminetetraacetic acid (L-6) N- (2-hydroxyethyl) -1,3-propanediaminetetraacetic acid (L-6) -7) 1,3-Propanediaminetetrakismethylenephosphonic acid (L-8) 2-Hydroxy-1,3-propanediaminetetrakismethylenephosphonic acid (L-9) 2,2-Dimethyl-1,3-propanediamine Acetic acid (L-10) 2,4-butanediaminetetraacetic acid (L-11) 2,4-Pentanediaminetetraacetic acid (L-12) 2-Methyl-2,4-pentanediaminetetraacetic acid (L-1) As the ferric complex salts of the compounds of (L-12), sodium, potassium or ammonium salts of these ferric complex salts can be used. It can be used um salt arbitrarily. From the viewpoint of the effect of the present invention and the solubility, ammonium salts of these ferric complex salts are preferably used.

Among the above-mentioned compound examples, those particularly preferably used in the present invention are (L-1), (L-3),
(L-4), (L-5) and (L-9), with (L-1) being particularly preferred.

Next, the compound represented by the formula [M] will be described in detail.

[0107]

[Chemical 15]

A _{1 to} A ₄ are as defined above, and n is 1 to 8
Represents the integer. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (for example, ethylene, propylene, butylene, pentamethylene, etc.). Hydroxyl group as a substituent, carbon number 1 to
And the lower alkyl group of 3 (methyl group, ethyl group, propyl group) and the like.

Preferred specific examples of the compound represented by the above general formula [M] are shown below.

[0110]

[Chemical 16]

As the ferric iron complex salt of the compounds (M-1) to (M-7), a sodium salt, potassium salt or ammonium salt of the ferric iron complex salt of these compounds can be optionally used.

Among the ferric iron complex salts of the present invention, the ferric iron complex salt of the organic acid represented by the general formula [L] or [M] is most preferably used for achieving the effect of the present invention, and particularly (L
-1), (L-3), (L-4), (L-5), (L-
9), (M-1), (M-2) and (M-7), and particularly preferably (L-1) or (M-1).

Next, compounds represented by the general formula [N] are shown.

[0114]

[Chemical 17]

In the formula, R ₁ represents a hydrogen atom or a hydroxyl group,
n is 1 or 2, x is 2 or 3, y is 0 or 1, and the sum of x and y is always 3.

Preferred compounds represented by the general formula [N] are [N-1] and "N-2".

[0117]

[Chemical 18]

Next, the compound represented by the general formula [P] is shown.

[0119]

[Chemical 19]

In the formula, A _{1 to} A ₄ may be the same or different and each is —CH ₂ OH, —PO ₃ M ₁ M ₂ or —COOM ₃
Represents M ₁ , N ₂ or M ₃ represents a hydrogen atom, an alkali metal atom (eg sodium, potassium) or another cation (eg ammonium, methylammonium, trimethylammonium etc.). X is an alkylene group of a substituted or unsubstituted 2-6 carbon atoms - represents a _{- (B 1 O) n -B} 2. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.

Examples of the alkylene group represented by X include ethylene, trimethylene, tetramethylene and the like.
The alkylene group represented by B ₁ or B ₂ includes methylene, ethylene, trimethylene and the like. X, B
Examples of the substituent of the alkylene group represented by ₁ or B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group). n represents an integer of 1 to 8, and preferably 1 to 4. Specific preferred examples of the compound represented by formula [P] are shown below, but the invention is not limited thereto.

[0122]

[Chemical 20]

[0123]

[Chemical 21]

As the bleaching agent, the above general formula [L],
In addition to the iron complex salts of the compounds represented by [M], [N], and [P], ferric complex salts of the following compounds and the like can be used.

[A'-1] Ethylenediaminetetraacetic acid [A'-2] Trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] Dihydroxyethylglycinic acid [A'-4] Ethylenediaminetetrakismethylenephosphonic acid [A'-4] A'-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxy Ethyl ethylenediamine triacetic acid [A'-10] ethylenediamine dipropionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminoniacetic acid [A'-13] nitrilotripropionic acid [A'-14] tri Ethylene tetramine hexaacetic acid [A'-15] ethylene diami Tetrapropionic acid The amount of the ferric iron complex salt of an organic acid added is preferably in the range of 0.1 mol to 2.0 mol, and more preferably 0.15 to 1.5 mol / liter, per liter of the bleaching agent or the bleach-fixing agent. is there.

The bleaching agent, the bleach-fixing agent and the fixing agent include imidazole and its derivatives described in JP-A-64-295258 or compounds represented by the general formulas [I] to [IX] described in the specification. And, by containing at least one of these exemplified compounds, it is possible to exert an effect on promptness.

In addition to the above accelerators, the exemplified compounds described in JP-A-62-123459, pages 51 to 115 and JP-A-63-17445, pages 22 to 25 The exemplified compounds described in JP-A-53-95630 and JP-A-53-28426 can be similarly used.

In addition to the above, the bleaching agent or bleach-fixing agent may contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can.

When the processing agent according to the present invention is a fixing agent or a bleach-fixing agent, thiocyanates and thiosulfates are preferably used as the main fixing agent. The content of thiocyanate is preferably at least 0.1 mol / liter or more, more preferably 0.5 mol / liter or more, and particularly preferably 1.0 mol / liter or more when processing a color negative film.
It is more than mol / liter. The content of thiosulfate is preferably at least 0.2 mol / liter or more, and more preferably 0.5 mol / liter or more when a color negative film is processed. Further, in the present invention, the object of the present invention can be achieved more effectively by using thiocyanate and thiosulfate in combination.

The fixing agent or bleach-fixing agent according to the present invention may contain, in addition to these fixing main agents, a pH buffering agent composed of various salts, alone or in combination of two or more kinds. Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Further, compounds known to be added to ordinary fixing agents or bleach-fixing agents such as alkylamines and polyethylene oxides can be appropriately added.

A fixing agent or a bleach-fixing agent is described in JP-A 64-2.
It is preferable to add the compound represented by the following general formula [FA] described on page 56 of the specification of No. 95258 and its exemplified compounds, and not only the effects of the present invention can be better exhibited but also a small amount of a light-sensitive material can be used for a long period of time. Another effect is that the amount of sludge generated in the processing liquid having fixing ability during the entire processing is extremely small.

[0132]

[Chemical formula 22]

The compound represented by the general formula [FA] described in the above specification is described in US Pat. No. 3,335,161 and US Pat.
It can be synthesized by a general method as described in 0,718. These compounds represented by the above general formula [FA] may be used alone or in combination of two or more kinds.

Good results are obtained when the amount of the compound represented by the general formula [FA] added is in the range of 0.1 g to 200 g per liter of the treatment liquid.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant for ferric ions of 8 or more. Here, the chelate stability constant is described by LG Sillen and AEMartell, “Stability Constant.
s of Metalion Complexes ”, The Chemical Society,
London (1964). S.Chaberek AEMartell, "Organ
ic Sequestering Agents ”, Wiley (1959) and the like.

As a chelating agent having a chelate stability constant for ferric ions of 8 or more, Japanese Patent Application No. 2-234776,
Examples thereof include those described in No. 1-324507. The amount of these chelating agents used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the stabilizer, which gives good results.

As a preferable compound added to the stabilizer, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds. Addition amount of ammonium compound is 0.00 per 1 liter of stabilizer
The range of 1 mol to 2.0 mol is preferable, and 0.00 is more preferable.
It is in the range of 2 to 1.0 mol.

Further, the stabilizer preferably contains sulfite.

Furthermore, the stabilizer preferably contains a metal salt in combination with the chelating agent. Examples of such metal salts include Ba, Ca, Ce, Co, In, La and M.
n, Ni, Bi, Pb, Sn, Zn, Ti, Zr, M
There is a metal salt of g, Al or Sr, which can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate or a water-soluble chelating agent. The amount used is preferably in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and more preferably 4 × 10 ⁻⁴ to 2 × 10 ⁻² mol, per liter of the stabilizer.

The stabilizers include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate salts, borate salts, hydrochloride salts, sulfate salts, etc.) and the like. It can be added. In the present invention, known antifungal agents can be used alone or in combination as long as the effects of the present invention are not impaired.

In the present invention, when the silver halide color photographic light-sensitive material is exposed for image and then continuously processed using an automatic developing machine, the method for replenishing the color development processing tank is as follows. A method of adding and dissolving it in a dissolving part provided at a portion in contact with the development processing solution is adopted.

That is, the automatic developing machine (automatic developing machine) preferably used in the present invention includes a processing tank (main tank) for processing a silver halide color photographic light-sensitive material and a dissolving section (sub-tank) for dissolving a solid processing agent. And is circulated between the processing tank and the dissolution section. In the melting part, impurities mixed in the supplied solid processing agent,
It is preferable to have a filtering means that prevents insoluble matter or undissolved matter from flowing into the processing tank.

When the solid processing agent is added to the dissolution section,
Replenishing the minimum evaporation amount of water is a preferable mode for carrying out the present invention. That is, the processing liquid tank at a certain temperature always evaporates, and unless water is replenished, the liquid surface decreases and becomes thicker, which causes deterioration of photographic performance, precipitation, tar, and the like. Therefore, it is necessary to supply the minimum amount of water to keep the liquid level in the tank.

Further, in the replenishment of water, it is necessary to consider taking-out by the photosensitive material in addition to the evaporated portion, and especially in the color developing tank, it is necessary to replenish the water in consideration of taking-out by the photosensitive material in addition to the evaporated portion. However, if too much water is replenished, it is not preferable for the effect of the present invention, and there is a problem that the amount of waste liquid increases. Therefore, the amount of water replenishment should be 5% or less, preferably 3%, with respect to the processing tank tank.
It is a preferred embodiment of the present invention to set the following.

The automatic developing machine has a detecting means for detecting the processing amount of the silver halide color photographic light-sensitive material, and the supplying device for automatically supplying the solid processing agent to the dissolving part according to the processing amount and the water supply are provided. It is preferable to have a water replenishing device.

In the present invention, there are provided a processing section for processing a light-sensitive material and a dissolving section for dissolving a solid processing agent, and the dissolving section is arranged at a portion in contact with the processing liquid of the processing section,
Moreover, by using an automatic developing machine having a dissolving means, it is possible to substantially eliminate the manual dissolving work which has been conventionally performed, and a replenishing tank or a replenishing tank which occupies about half of the developing machine. It is even possible to eliminate the pumps for replenishment and liquid feeding, and it is possible to significantly reduce the cost and downsize the device or equipment. However, since the treating agent is dissolved in the dissolving portion, even the solid treating agent can be rapidly dissolved, a local increase in concentration can be prevented, and the treating agent can be made uniform throughout the treating portion.

When there is no dissolution part, for example, when tablets or granules are directly added to a tank treatment tank or a replenishment tank, the initial solubility is slightly good, but the dissolution rate is slow, and the alkali agent etc. harden to dissolve easily. However, since it accumulates at the bottom of the tank, the phenomenon of increasing the concentration of the photographic processing agent occurs locally, and tar and insoluble substances are produced, which seriously affects the photographic performance and clogging of the circulation system.

Further, in the present invention, since the photographic processing agent is a solid processing agent, the parts agent may scatter during the work and adhere to or be contaminated with the human body, particularly hands, clothes and peripheral equipment. In addition, it is possible to supply an environmentally compatible processing agent that does not require a plastic bottle.

Further, by providing the treating agent supplying means in the dissolving section of the automatic developing machine, the processing agent is not manually put into the dissolving section, and the working efficiency is greatly improved.

In carrying out the processing method of the present invention, a processing agent having a bleaching ability, a processing agent having a fixing ability, a stabilizing agent and the like are used in addition to the above color development processing agents. Is not particularly limited.

Next, the light-sensitive material to which the processing agent of the present invention is applied will be described.

When the light-sensitive material is a light-sensitive material for photographing, silver iodobromide or silver iodochloride having an average silver iodide content of 3 mol% or more is used as the silver halide grains, but particularly 4 mol% From the above, silver iodobromide containing up to 15 mol% of silver iodide is preferable. Above all, the average silver iodide content of the present invention is preferably 5
% To 12 mol%, most preferably 8 to 11 mol%.

As the silver halide emulsion used in the light-sensitive material processed with the photographic processing agent of the present invention, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The following shows the locations.

[Item] [Page of RD308119] Iodine structure 993 IA Item Manufacturing method 993 I-A item and 994 E item Crystal habit Normal crystal 993 I-A Twin crystal 〃 Epitaxial 〃 Halogen composition Uniform 993 I- Item B Non-uniform 〃 Halogen conversion 994 IC item 〃 Substitution 〃 Metal-containing 994 Item ID Monodisperse 995 Item IF Addition of solvent 〃 Latent image forming position Surface 995 Item internal 〃 Applicable negative material 995 Item I-H Positive (including internal fog grains) 〃 Mix and use emulsions 995 Item I-J Desalting 995 Item II-A Silver halide emulsions that have been physically ripened, chemically ripened and spectrally sensitized use. Additives used in such processes are Research Disclosure No.17643, No.187.
16 and No. 308119 (Respectively RD17643, RD1871
6 and RD308119).

The places described in the table below are shown.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I , J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Photographic additives are the same as above. It is described in Research Disclosure. The following table shows the relevant locations.

[Items] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII C, XIII C Section 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 25-26 650 Matting agent 1007 X VI Developer (contained in light-sensitive material) 1011 XX-B Item Treated with the photographic processing agent of the present invention Various couplers can be used in the light-sensitive material, and specific examples thereof are described in Research Disclosure above. The following table shows the relevant locations.

[Item] [Page of RD308119] [RD 17643] [RD 18716] Yellow coupler 1001 Item VII-D Item VII C to G Magenta coupler 1001 Item VII-D Item VII C to G Cyan Coupler 1001 VII-D Item VII C to G DIR coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F alkali-soluble coupler 1001 VII-E Additive is RD308119 XIV It can be added by the described dispersion method or the like.

In the present invention, the above-mentioned RD17643 No. 28 is used.
The supports described on page RD18716, pages 647-648 and RD308119, XIX can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119 VII-K. The photosensitive material is RD308119 VII-K.
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section can be adopted.

Next, the light-sensitive material for color printing which is preferable for applying the photographic processing agent of the present invention will be described.

As the silver halide grains in the light-sensitive material, silver halide grains mainly containing silver chloride containing at least 80 mol% of silver chloride are used, preferably 90 mol% or more,
Particularly preferably, those containing 95 mol% or more, and most preferably those containing 99 mol% or more are used.

The silver halide emulsion mainly containing silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less. Is preferable, more preferably 10 mol% or less, further preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Below, it is most preferably zero. Such silver chloride 50
The silver halide grains mainly composed of silver chloride containing more than mol% are
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all light-sensitive silver halide emulsion layers.

The crystals of the silver halide grains may be normal crystals, twin crystals or other crystals, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layer (phase) -like structure (core-shell type) having different inside and outside. Good. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used. Further, silver halides described in JP-A 64-26837, 64-26838, 64-77047 and the like can be used.

Further, the silver halide grains are prepared by the acidic method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Alternatively, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

[0167]

【Example】

Example 1 A fixing tablet for a color negative film was prepared according to the following procedure.

125 g of ammonium thiosulfate, 7.5 g of sodium sulfite, 7.5 g of potassium carbonate and 1 g of ethylenediaminetetraacetic acid 2Na salt were added in an air jet fine pulverizer to give an average particle size of 10
Grind to μm. This fine powder was granulated in a commercially available fluidized bed spray granulator for about 7 minutes at room temperature by spraying 1.5 ml of water, and then the granulated product was dried in vacuum at 40 ° C. for 8 hours. To almost completely remove the water content of the granulated product. The prepared granulated product is uniformly mixed for 10 minutes using a mixer in a room whose humidity is controlled to 40% RH or less at 25 ° C. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, so that the filling amount per tablet was 9.3 g.
0 fixer replenishing tablets for color negatives were made.

Furthermore, the surface of the tablet was spray-coated with the water-soluble polymer shown in Table 1 (however, the molecular weight was about 50,000). However, the compound group F shown in Table 1 is contained in the water-soluble polymer to be sprayed. The content is shown as a ratio with the polymer.

These tablets were stored under the conditions of 30 ° C. and 80% for 3 weeks, and two tablets were dissolved in 100 ml of water to measure the sulfite concentration, and the results were compared with those before storage. The dissolution speed was also measured. Further, the surface condition of the tablet after storage was observed and evaluated according to the following evaluation criteria.

◯: No change Δ: Sweating ×: Tablet shape collapsed The results are shown in Table 1.

[0172]

[Table 1]

As can be seen from Table 1, those having the constitution of the present invention have sufficient residual sulfurous acid, good solubility and good storage stability.

Solubility Evaluation ◯: Dissolved within 10 minutes Δ: Dissolved within 10 to 30 minutes ×: 30 minutes or more Example 2 A processed tablet for a color negative film was prepared according to the following procedure.

1) Color development replenishment tablet operation for color negative (1) 16.3 g of developing agent CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] Grind in a grinder until the average particle size is 10 μm. This fine powder in a commercially available fluidized bed spray granulator for about 7 minutes at room temperature,
After granulating by spraying 0.63 ml of water,
Dry at 63 ° C for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (2) 8 g of hydroxylamine sulfate is pulverized and granulated in the same manner as in operation (1). The amount of water sprayed is 0.33 ml, and after granulation, 60 ℃
Dry for 7 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (3) 1-Hydroxyethane-1,1-diphosphonate disodium salt 7.5
g, sodium sulfite 10 g, potassium carbonate 87.5 g, sodium hydrogen carbonate 7.5 g, sodium bromide 1 g, and diethylenetriamine pentaacetic acid 7.5 g were pulverized in the same manner as in (1),
Mix evenly with a commercially available mixer. Then, in the same manner as in (1), the amount of water sprayed is set to 25 ml and granulation is performed. After granulation, the granulate is dried at 70 ° C. for 15 minutes and then the granulate is dried in vacuum at 40 ° C. for 2 hours to remove almost completely the water of the granulate.

Operation (4) The granules prepared in the above operations (1) to (3) are 40% at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to RH or less. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 5.8 g, to prepare 20 color development replenishing tablets for color negative.

Further, the surface of the tablet was sprayed and coated with a water-soluble polymer (molecular weight: about 50,000) shown in Table 2. However, the water-soluble polymer to be sprayed contains one selected from the compound group F. The content is shown as a ratio with the polymer.

The same evaluation as in Example 1 was performed. However, the residual CD-4 concentration was measured. However, the surface condition of the tablets after storage was evaluated as ◯: no change, Δ: slightly blackened, and ×: blackened and lost shape.

The results are shown in Table 2.

[0182]

[Table 2]

As can be seen from Table 2, even in the case of the color negative color developing agent, the constitution of the present invention exhibits good performance.

Example 3 1) Color development replenishing tablet for color paper Operation (A) Developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β-
16 g of (methanesulfonamide) ethyl] aniline sulfate] are pulverized in an air jet fine pulverizer until the average particle size becomes 10 μm. The fine powder is granulated by spraying 0.6 ml of water in a commercially available fluidized bed spray granulator at room temperature for about 5 minutes, and then the granulated product is dried at 60 ° C. for 8 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (B) 16 g of disulfoethylhydroxylamine disodium salt
Is pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 0.
After making up to 4 ml, granulate and dry at 50 ° C for 10 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (C) 4.0 g of Tinopearl SFP (manufactured by Ciba Geigy), 0.5 g of sodium sulfite, 47 g of potassium carbonate, 0.0 g of potassium bromide
After pulverizing 4 g, 3.3 g of diethylenetriamine pentaacetic acid, 40 g of sodium p-toluenesulphonate and 2.7 g of potassium hydroxide in the same manner as in (A), they are uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water sprayed is set to 26.7 ml and granulation is performed. After granulation, the granulated product is dried at 70 ° C for 15 minutes,
Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (D) The granules prepared in the above operations (A) to (C) are 40% at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to RH or less. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressto Correct 1527 HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 7.85 g, to prepare 20 color development replenishing tablets for color paper.

The same evaluation as in Example 2 was performed.

The results are shown in Table 3.

[0190]

[Table 3]

As can be seen from Table 3, even in the case of a color paper color developing agent, the composition of the present invention exhibits good storability.

Example 4 With respect to the bleach-fixing agent for color paper, the same experiment as in Example 1 was conducted and the same result was obtained.

Example 5 Example 1 The same experiment was conducted by changing the molecular weight of the water-soluble polymer in Experiment No. 1-5 as follows.

The results are shown in Table 4.

[0195]

[Table 4]

As is clear from Table 4, the water-soluble polymer of the present invention preferably has a molecular weight in the range of 3,000 to 50,000.

Example 6 [Color negative processing step] Next, a method of processing a light-sensitive material using the automatic developing machine of the present invention will be described below.

Konica Color Negative Film Processor CL
-The tablet processing function, liquid level detection function, hot water supply function, etc. were installed on the KP-50QA by modification, and the following treatment experiments were conducted. The table below shows the standard processing conditions for the automatic processing machine.

Processing process Temperature Time Color development 38 ± 0.3 ℃ 3 minutes 15 seconds Bleach 38 ± 1.0 ℃ 45 seconds Fixing -1 38 ± 1.0 ℃ 45 seconds Fixing-2 38 ± 1.0 ℃ 45 seconds Stability -1 38 ± 3.0 ℃ 20 seconds Stability-2 38 ± 3.0 ℃ 20 seconds Stability-3 38 ± 3.0 ℃ 20 seconds Drying 60 ℃ 60 seconds Stabilizer is replenished in the 3rd tank, and the overflow liquid flows into 2 tanks and 1 tank sequentially. It is a method.

Preparation of the automatic processing liquid was carried out by the following method.

Color developing tank liquid (21.0 liters) 15 liters of warm water at 35 ° C. was placed in the developing machine color developing tank, and 399 color developing replenishing tablets for color negative film prepared in the same manner as in 2 were charged and dissolved. Next, 21 tablets were separately tableted as starter ingredients, and after starting dissolution, warm water was added up to the tank mark line to complete the tank solution.

Color development starter for color negative Sodium bromide 0.8 g Sodium iodide 2.0 mg Sodium hydrogencarbonate 3.0 g Potassium carbonate 0.5 g Bleaching solution (5.0 l) 3.0 l of 35 ° C. warm water was put in the automatic bleaching tank, and the following was added. 350 bleach replenishment tablets for color negative film made by the method
Individually added and dissolved. Next, 10 starters of the following formulation, which were separately tabletted as starter components, were added, and after dissolution, warm water was added up to the tank mark to complete the tank solution.

Bleaching Replenishing Tablet for Color Negative 1,3-Propanediaminetetraacetic Acid Ferric Ammonium Monohydrate
Pulverize and granulate with 175 g, 60 g of succinic acid, 73 g of maleic acid and 2 g of 1,3-propanediamine tetraacetic acid in the same manner as in the operation (1). The amount of water sprayed is 5.0 ml, and after granulation, it is dried at 60 ° C. for 7 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

80 g of potassium nitrate, ammonium bromide 200
Grain and granulate 60 g of potassium carbonate in the same manner as in step (1). The amount of water sprayed is 1.0 ml, and after granulation, it is dried at 70 ° C. for 3 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

The prepared granulated product is uniformly mixed for 10 minutes by using a mixer in a room whose humidity is controlled to be 40% RH or less at 25 ° C.
Next, mix the mixture with Kikusui Seisakusho Tough Press Collect 1527HU.
The tablet was recompressed with a modified tableting machine to a filling amount of 6.5 g to perform compression tableting to prepare 80 color negative bleaching replenishing tablets.

Bleach Starter for Color Negative Sodium Bromide 10.0g Sodium Bicarbonate 1.5g Potassium Carbonate 3.5g Fixing Solution (4.5l for the first tank, 4.5l for the second tank) Automobile fixing tank 35 for the first and second tanks 3 ° C warm water each.
Then, 112 tablets of fixing replenisher for color negative film prepared in the same manner as in Experiment No. 1-5 of Example 1 were charged and dissolved. Next, hot water was added up to the tank mark to complete the tank solution.

Stabilizer (3.2 liters for each of the 1st to 3rd tanks) A color negative prepared as shown below by adding 3.0 liters of hot water at 35 ° C. to the 1st, 2nd, and 3rd tanks of the developing machine fixing tank. 40 tablets for stable replenishment for film were added and dissolved. Next, hot water was added up to the tank mark to complete the tank solution.

Next, during the temperature control of the automatic developing machine, 20 tablets of the respective supplemental tablets were set in the supplementary tablet supplying device provided to the automatic developing machine.
This replenishing tablet is fed one by one when two 135 size 24 film films are processed. At the same time, replenishing hot water from the hot water supply device is 40 ml in the color developing tank, 10 ml in the bleaching tank and 40 ml in the fixing tank. , 80 ml was supplied to the stabilizing tank.

4) Stable replenishing tablet for color negative m-hydroxybenzaldehyde 200 g, Emulgen 985;
10 g and 45 g of potassium carbonate are crushed and granulated in the same manner as in the operation (1). The amount of water sprayed is 3.0 ml, and after granulation, the granulated product is dried in vacuum at 30 ° C. for 8 hours to almost completely remove the water content of the granulated product.

The granulated product prepared by the above-mentioned operation was used at 25 ° C. and 40% R
Mix evenly for 10 minutes in a room conditioned below H using a mixer. Next, the mixture was filled with Kikusui Seisakusho's Tough Press Collect 1527HU using a tabletting machine with a modified filling amount per tablet.
The tablet was compressed to 0.2 g to prepare 1060 fixing replenishing tablets for color negative.

Color negative film SuperDD- manufactured by Konica Corporation
After exposing 100 to a conventional method, a running test was performed using the following automatic developing machine and treating agent.

<Automatic processor> The Konica Color Negative Film Processor CL-KP-50QA was provided with the tablet supply function, the liquid level detection function, and the hot water supply function shown in FIGS. .

FIG. 1 is a schematic view showing an example of an automatic developing machine used in the present invention, which is a simplified representation of the control mechanism of a color negative film processing apparatus.

When the color negative film is carried in from the photosensitive material insertion portion 13 and passes through the photosensitive material area detection sensor 7 and a certain area is detected, the replenishment processing agent replenishing device 8
The replenishing water replenishing device 10 and the solenoid valve 12 are operated by receiving a signal from the control unit 11, and the replenishing treatment agent and the replenishing water for liquid preparation are supplied to each treatment tank 1
・ The required amount will be supplied to 2/3/5.

When the temperature of the automatic processing machine is adjusted for several hours, the processing liquid in each of the processing tanks 1 to 5 is evaporated. Upon receiving the signal of 11, the replenishment water replenishing device 10 and the solenoid valve 12 are operated, and replenishment water is replenished until the upper limit detection mechanism of the liquid level detection sensor 9 operates. It is preferable that the wash warm water 14 that is the makeup water supplied by the makeup pipe 15 is temperature-controlled for both the liquid-conditioning makeup water and the evaporation-correction makeup water. In addition, each processing tank 1-5
1 is a color developing tank, 2 is a bleaching tank, 3 is a fixing tank, and 4.4.
Represents a washing tank and 5 represents a stabilizing tank. Further, 6 is a drying section.

FIG. 2 is a schematic explanatory view showing an example of the replenishment treatment agent replenishing device in the case where the replenishment treatment agent solidified into a tablet is used.

When the control unit 11 operates in response to the signal from the photosensitive material area detection sensor 7 and the solid replenishment processing agent replenishment cam 22 operates, the solid replenishment processing agent pushing claw 23 replenishes the solid state replenished in the cartridge 25. Treating agent 24 in each treatment tank
Filtration device in sub-tank 20 which is the replenishment processing agent dissolution part of No. 5
Supply one or several inside 21.

The replenished solid replenishing treatment agent 24 is gradually dissolved and supplied to the main treatment tank 16 of each treatment tank 1, 2, 3, 5 by the circulation pump 18.

The circulation pump 18 is used as the main processing tank.
If all or most of the circulation flow of the processing liquid 17 circulating between the sub tank 16 and the sub tank 20 is configured to directly pass through the filtering device 21 in the sub tank 20, the solubility of the supplementary processing agent 24 will be further increased. .

In the figure, 19 is a temperature control heater, 26 is a pushing spring for pressing and holding the replenishment processing agent 24 in the cartridge 25, 27 is the main processing tank 16 of each processing tank 1, 2, 3, 5 A communication pipe communicating with the sub tank 20, 28 is a processing rack, and 29 is an overflow port.

FIG. 3 is a schematic explanatory view showing an example of the makeup water supply section. Also in FIG. 3, as in FIG.
Is used in the form of tablets.

In response to the signal from the photosensitive material area detection sensor 7, the control unit 11 operates, the solid replenishment processing agent replenishment cam 22 and the solid replenishment processing agent pushing claw 23 operate, and the solid state solid photographic processing agent 24 is replenished. At the same time, the makeup water replenishing device 10 and the solenoid valve 12 are activated to replenish the makeup water. The replenishment amount of the replenishment water for liquid preparation can be solved by previously inputting the operating time of the solenoid valve 12 and the replenishment water replenishing device 10 to the control unit 11 in an amount more than that required to dissolve the replenishment treatment agent 24.

[0223] Further, the processing tanks 1 to
When the processing liquid 17 of 5 causes the liquid level to drop due to evaporation,
The liquid level detection sensor 9 detects the lowered liquid level, transmits a signal to the control unit 11, operates the solenoid valve 12 and the makeup water replenishing device 10, and replenishes the makeup correction makeup water to the normal liquid level. To do. When reaching the regular liquid level, the liquid level detection sensor 9 detects the regular liquid level, transmits a signal to the control unit 11, and stops the operation of the solenoid valve 12 and the makeup water replenishing device 10.

Next, during the temperature control of the automatic developing machine, 20 tablets each of the supplementary tablets previously prepared were set in the supplementary tablet supplying device provided to the automatic developing machine.

This replenishing tablet is 13 for a color developing tank.
When 5 pieces of 5 size 24 shot film are processed, 2 pieces are put in each, and in another tank, 2 pieces are put in 1 piece each, and at the same time, replenishing hot water is supplied from the hot water supply device to the color developing tank.
40 ml, 10 ml for bleaching tank, 40 ml for fixing tank, 80 for stabilizing tank
It was set to be supplied in ml.

In the running test, 0.05 rounds per day were continuously processed until the total amount of replenishing water for the color developing solution was twice the capacity of the color developing tank solution (2 rounds). After the running was completed, the minimum transmission density of the unexposed area and the transmission density of the maximum density area of the color negative sample were measured using PDA-65 (manufactured by Konica). After the running was completed, the state of tar generation in the tank was observed. It evaluated as follows.

◯: No tar was generated Δ: Occurred on the vessel wall ×: Occurred on the entire liquid interface Table 5 shows the results.

[0228]

[Table 5]

As is clear from Table 5, when the water-soluble polymer of the present invention and the compound selected from the compound group F are contained, no tar is generated and no stain is generated, and a stable treatment is possible.

Example 7 In preparing a fixing solution tablet in Example 5, the treatment was carried out by changing the compounds selected from the water-soluble polymer and the compound group F as shown in Table 5. The tablet for color developing solution was prepared in the same manner as in Experiment No. 4-2. The same treatment as in Example 6 was performed, and the tank liquids of the first tank of fixing and the first tank of stabilizing liquid after the treatment were observed and evaluated according to the following evaluation criteria.

◯: No precipitation or floating material was generated. Δ: No precipitation was generated, but floating material was generated. X: Floating material was generated, and some precipitation was found. Table 6 shows the results.

[0232]

[Table 6]

As is clear from Table 6, when the constitution of the present invention is adopted, no precipitation is generated and a good treatment can be provided.

[0234]

INDUSTRIAL APPLICABILITY According to the present invention, it has a working environment suitability without skin sensitization trouble, and has improved storage stability of tablet processing agents, especially internal reaction in tablets and improvement of tablet deterioration and dissolution speed resulting therefrom. It is possible to provide an improved tablet-like processing agent for a silver halide photographic light-sensitive material.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing an example of an automatic developing machine used in the present invention.

FIG. 2 is a schematic explanatory view showing an example of a replenishment section for a solidified replenishment treatment agent.

FIG. 3 is a schematic explanatory view showing an example of a makeup water supply unit.

[Explanation of symbols]

 1 Color developing tank 2 Bleaching tank 3 Fixing tank 4 Washing tank 5 Stabilizing tank 5 Drying section 6 Drying area 7 Photosensitive material area detection sensor 8 Replenishment processing agent replenishing device 9 Liquid level detection sensor 10 Replenishing water replenishing apparatus 11 Control section 12 Electromagnetic valve 13 Photosensitive material Insertion part 14 Washing hot water 15 Supply pipe 16 Main processing tank 17 Processing liquid 18 Circulation pump 19 Temperature control heater 20 Sub tank 21 Filtration device 22 Solid replenishment processing agent replenishing cam 23 Solid replenishment processing agent push claw 24 Replenishment processing agent (solid photographic processing agent) ) 25 Cartridge 26 Push spring 27 Communication pipe 28 Processing rack 29 Overflow port

Claims (2)

[Claims] 1. A tablet form characterized by being coated with a coating material containing at least a water-soluble polymer containing at least a compound represented by the general formula (I) as a constituent and at least one compound selected from the compound group F. Processing agent for silver halide photographic light-sensitive materials. [Chemical 1] Wherein, R ₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, R ₂ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms. ] Compound Group F Glycols Glycerin esters Sucrose fatty acid esters Castor oil organic acid esters Carbitols Cersolves sorbitans 2. A coating material containing at least a water-soluble polymer containing at least the compound represented by the general formula (I) as a constituent component and at least one selected from the compound group F. A processing method using a tablet-form silver halide photographic light-sensitive material processing agent.