JPH061356B2 - Method for storing developer with improved storage stability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for storing a developer for silver halide photographic light-sensitive materials, and more particularly, a method for storing a developer for obtaining a high-contrast image useful in the field of photoengraving. It is about.

[Conventional technology]

In the field of photoengraving, a rapid-access developer (black-and-white high-contrast developer) has been widely used in recent years.

The developer for rapid access includes hydroquinone as a developing agent and a super-additive developing agent (usually 1-phenylpyrazolidones or p-aminophenol compounds),
A developer containing sulfite as a preservative, carbonate as a buffer agent, other antifoggants, a solvent and the like.

Despite the high concentration of sulfite contained in the developer, the developer has a higher pH than the lith developer, so that the developer is relatively easily oxidized during long-term storage or storage in a hot and humid environment. It is known that it will be done.

The storage method of the developer is usually left in a warehouse or outdoors under adverse conditions as compared with silver halide photographic light-sensitive materials.
It is desired to be stable even under such adverse conditions.

The rapid access developer is not only of a type that can be used as it is for ease of use, but also of a concentrated type that is used after being concentrated as much as possible for transportation convenience and cost. In this case, the greater the amount of sulfite, the lower the concentration,
Furthermore, since the pH will increase, it is not possible to administer an amount of sulfite that further maintains the homeostasis, and another good method for preservation is required.

Focusing on the oxygen permeability of the packaging material, JP-A-47-243
No. 23 and No. 61-73147, it has been proposed to encapsulate the developer with a packaging material having low air permeability.

However, we have found that pursuing oxygen permeability cannot be regarded as a preferable method for storing a developer. This is because the storability is never good when the developer is encapsulated using the packaging material made of the synthetic organic polymer material described in the above document and stored under high temperature and high humidity. It is considered that this is because oxygen easily permeates under high humidity and the storage stability is deteriorated by other factors. Therefore, a packaging material that is more suitable for storing the developer is desired.

[Object of the Invention]

An object of the present invention is to provide a method for stably storing a high pH developer containing a developing agent, a preservative and an alkaline agent.

[Structure of Invention]

The object of the present invention is to (a) a developing agent and (b) a sulfite salt of 0.3.
In the method for preserving a developing solution, the developing solution containing at least a mol / mol, and (c) an alkaline agent for adjusting the pH of the developing solution to 10 or more is stored in a container made of an organic polymer packaging material. The organic polymer of the layer composed of at least two layers, which is in contact with the developing solution among the plurality of layers, is represented by the following general formula [a], and the organic polymer of at least one layer of the other layers is represented by the following general formula [b]. ] Or [c], it is achieved by a method for storing a developer.
Further, when the organic polymer of the outermost layer of the plurality of layers is represented by the following general formula [a], the object of the present invention can be achieved to a higher degree.

General formula [a] In the formula, X and Y each represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group or an alkyl group,
n represents an integer of 100 or more.

General formula [b] In the formula, p and q each represent an integer of 1 to 12, and m is 1
Represents an integer of 00 or more.

General formula [c] In the formula, r represents an integer of 1 to 12, and l represents an integer of 100 or more.

In the general formula [a], the alkyl group represented by X and Y may be linear or branched, preferably has 1 to 5 carbon atoms, and may be substituted with a halogen atom, a hydroxyl group or a carboxyl group, n is It is preferably 10,000 or less.

In the general formula [b], m is preferably 10,000 or less, and in the general formula [c], l is preferably 10,000 or less.

The following can be mentioned as specific examples of the compound represented by the general formula [a].

(a-1) (a-2) (a-3) (a-4) (a-5) (a-6) (a-7) The following can be mentioned as specific examples of the compound represented by the general formula [b].

(b-1) (b-2) (b-3) (b-4) The following can be mentioned as specific examples of the compound represented by the general formula [c].

(c-1) (c-2) (c-3) (c-4) In the present invention, the above general formula [a], [b] or [c]
The organic polymer represented by can be easily synthesized from a monomer by homopolymerization, copolymerization or polycondensation. In these general formulas, the terminal group is not shown,
Included are those that normally occur in such polymerization reactions.

The thickness of each of the above single layers constituting the organic polymer packaging material of the present invention is preferably in the range of 10 to 200 μm, and the total laminated film thickness is more preferably in the range of 30 to 600 μm. More preferably, each single layer has a thickness of 2
0 ~ 100μm, the total film thickness is 60 ~ 300μm
It is in the range of.

When the thickness of each of the above single films constituting the organic polymer packaging material of the present invention is 10 μm or less, the storage stability of the developing solution is poor and the strength is small as a container for enclosing 10 of the developing solution.
It is preferable that the thickness is 200 μm or more, and if the thickness is 200 μm or more, the packaging material has poor flexibility and does not deform according to the amount of the developer inside, so that air easily accumulates in the dead space under the lid. Therefore, the storability of the developer is deteriorated.

The laminated organic polymer packaging material in the present invention is preferably 10 to 200 μm of the compound represented by the general formula [a].
Preferably, a thin film of the compound represented by the general formula [b] or [c] having a thickness of 10 to 200 μm is directly laminated on the thin film of (1) or laminated by heat contact or an adhesive (so-called lamination), or further on the general formula A thin film of the compound represented by [a] can be obtained by stacking or laminating as described above.

The container made of the packaging material of the present invention may be made of a single layer of the packaging material, and is further covered with the packaging material in a single layer or a double layer, that is, a container made of a double layer or a triple layer of the packaging material. However, the effect of the present invention can be further enhanced according to the double or triple mode.

When the packaging material of the present invention has a laminated structure consisting of three layers,
The material forming the outermost layer can be arbitrarily selected, but as described above, the organic polymer of the layer is preferably selected from the compounds represented by the general formula [a].

In a preferred embodiment of the present invention, the packaging material has a layer structure of 3 layers or 4 layers, and the organic polymer of the innermost layer and the outermost layer of these layers is represented by the general formula [a]. And an organic polymer of at least one layer other than these two layers is represented by the general formula [b] or [c].

The following developing agents are included in the developing solution to which the method of the present invention is applied.

Typical examples of HO- (CH = CH) n-OH type developers include catechol, pyrogallol and its derivatives, and ascorbic acid. Hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2 , 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-
Diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl -Pyrogallol, 4-
(2'-hydroxybenzoyl) pyrogallol, sodium ascorbate and the like.

Further, HO (CH = CH) The n-NH ₂ type developer, ortho and aminophenol or aminopyrazolone of para are exemplary, 4-aminophenol,
2-amino-6-phenylphenol, 2-amino-4
-Chloro-6-phenylphenol, 4-amino-2-
Phenylphenol, 3,4-diaminophenol, 3
-Methyl-4,6-diaminophenol, 2,4-diaminoresorcinol, 2,4,6-triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p- Examples include hydroxyphenylaminoacetic acid and 2-aminonaphthol.

Furthermore, As, for example, 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N- (4-amino-3-methylphenyl)-
Morpholine, p-phenylenediamine, 4-amino-
N, N-diethyl-3-hydroxyaniline, N, N,
N ', N'-tetramethylparaphenylenediamine, 4
-Amino-N-ethyl-N- (β-hydroxyethyl)
-Aniline, 4-amino-3-methyl-N-ethyl-N
-(Β-hydroxyethyl) -aniline, 4-amino-
N-ethyl- (β-methoxyethyl) -3-methyl-aniline, 4-amino-3-methyl-N-ethyl-N-
(Β-methylsulfonamidoethyl) -aniline, 4-
Amino-N-butyl-N-γ-sulfobutylaniline,
1- (4-aminophenyl) -pyrrolidine, 6-amino-1-ethyl-1,2,3,4-tetrahydroquinone, 9-aminourolidine and the like are available, and examples of the heterocyclic type developer include 1- Phenyl-3-pyrazolidone, 1
-Phenyl-4-amino-5-pyrazolone, 1- (p-
Aminophenyl) -3-amino-2-pyrazoline, 1-
Phenyl-3-methyl-4-amino-5-pyrazolone,
5-aminouracil etc. can be mentioned.

In addition, TH James by The Theory of the
The Theory of the Fourth Edition
Photographic Process, Fourth Edition) pages 291-334 and Journal of the American Chemicals.
Society (Journal of the American Chemical Socie
ty) The developer described in Vol. 73, page 3100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more,
It is preferable to use two or more kinds in combination.

Examples of the sulfite salt contained in the developer to which the method of the present invention is applied include sodium sulfite, potassium sulfite, ammonium sulfite, and the like which are usually used in the developer. The developer may contain hydroxylamine or a hydrazide compound as a preservative.

Examples of the alkaline agent for adjusting the pH of the developing solution to which the method of the present invention is 10 or more include caustic alkali (eg sodium hydroxide, potassium hydroxide), alkali carbonate (eg sodium carbonate, potassium carbonate), amine. Etc. Alkaline agents usually used in developing solutions are mentioned.

Other buffer agents with pH as used in general black and white developers, inorganic development inhibitors such as bromcali, organic development inhibitors such as benzotriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, benzyl alcohol, polyalkylene oxide Development accelerator,
Addition of surface active agents such as sodium alkylaryl sulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin and glyoxal, ionic strength modifiers such as sodium sulfate. Is optional.

Hereinafter, the present invention will be described more specifically with reference to examples. The technical scope of the present invention is not limited to the following examples, and various embodiments can be applied.

〔Example〕

Preparation of Test Photosensitive Material A silver halide photographic photosensitive material was prepared according to Comparative Example 3 of JP-B-59-50976.

Preparation of Developers Concentrated solutions A and B were prepared according to the following prescription.

Formulation of developer (concentrate A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylenediglycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1 -Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount that adjusts the pH of the solution to 10.6 Potassium bromide 4.5g (Concentrated solution B) Pure water (ion-exchanged water) 3ml Diene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer is used, the concentrate A and the concentrate B are dissolved in 500 ml of water in this order, and the solution is finished to 1.

Preparation of developer storage container A packaging material having a layer structure and a film thickness of 10 shown in Table 1 below was prepared.

10 of the above concentrated solution A was sealed in the above container and stored at high temperature and high humidity (1 at 65 ° C. and 90% relative humidity in a thermo tester tank).
After storing for a week), a working solution was prepared and the change in photographic performance was examined using the above-mentioned light-sensitive material.

Regarding the photographic performance, after exposure through an optical wedge for sensitometry, a developing solution was processed by an automatic developing machine using a solution used according to the above-mentioned developing solution formulation. A commercially available fixer for rapid access was used as the fixer.

Processing conditions Development 33 ° C 20 seconds Fixing 30 ° C 20 seconds Washing with water 25 ° C 20 seconds Drying 50 ° C 20 seconds Photographic performance is indicated by sensitivity, and a concentration of 2.0 is obtained when processed with a working solution prepared using a concentrate immediately after preparation. It is shown as a relative value with the reciprocal of the exposure amount required for 100 as 100. The results are shown in Table 2.

As is clear from Table 2, the developer enclosed in the packaging material according to the present invention is
It can be seen that the sensitivity is not significantly reduced even when stored under high temperature and high humidity. From this, it is presumed that the storage performance can be further improved when the packaging material according to the present invention is double or triple-layered.

[Effect of the Invention] Developing agent, sulfite 0.3 mol / or more, and p of the developing solution.
By using the packaging material according to the present invention as a packaging material for a developer containing at least an alkaline agent for making H 10 or more, compared with the case of using a known packaging material,
The storability of the developer is improved.

Claims (2)

[Claims] 1. A developer containing a developer, a sulfite salt of 0.3 mol / mol or more, and an alkaline agent for adjusting the pH of the developer to 10 or more in a container made of an organic polymer packaging material. In the storage method, the packaging material is composed of at least two layers, the organic polymer of the layer in contact with the developer is represented by the following general formula [a], and the organic polymer of at least one layer of the other layers is represented by the following general formula [a]. b] or [c], which is a method for storing a developing solution. General formula [a] [In the formula, X and Y each represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group or an alkyl group, and n represents an integer of 100 or more. ] General formula [b] [In the formula, p and q each represent an integer of 1 to 12, and m represents an integer of 100 or more. ] General formula [c] [In the formula, r represents an integer of 1 to 12, and l represents an integer of 100 or more. ] 2. The other layer comprises at least two layers, and the organic polymer in the outermost layer of these layers is represented by the general formula [a].
The method for storing the developer according to the item.