JPS6363037A - Method for preserving liquid developer which is improved in shelf life - Google Patents

Abstract

PURPOSE:To enable stable preservation of a high-pH liquid developer contg. a developing agent, preservative and alkali agent by forming a packaging material into at least two layers and constituting said material of a specific org. high polymer. CONSTITUTION:The packaging material is formed of at least two layers in a liquid developer preserving method for storing the liquid developer contg. at least the developing agent, >=0.3mol/l sulfite and the alkali agent to adjust the pH of the liquid developer to >=10 into a container made of the packaging material. The org. high polymer of the layer in contact with the liquid developer is expressed by formula [I] and the org. high polymer of at least one of the other layers is expressed by formula [II] or [III]. The thickness of the respective single layers constituting the org. high polymer packaging material are respectively preferably in a 10-200mum range and the total thickness of the laminated films is more preferably in a 30-600mum range.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for preserving a developer for silver halide photographic light-sensitive materials, and in particular a method for preserving a developer for obtaining a high contrast image useful in the field of photolithography. It is related to.

[Conventional technology]

In the photolithography field, in recent years rapid access development e, (
High-contrast black-and-white developers are increasingly being used.

The developer for RAVID ACCESS contains hydroquinone and a superadditive developing agent (IFFI, 1-phenylpyrazolidones or p-amino-77-7-ol compounds) as a developing agent, and sulfite and neutral compound as preservatives. - A developer containing carbonate as a reinforcement agent, other antifogging agents, solvents, etc.

Although this developer contains a high concentration of sulfites, it has a higher pH than the lithium developer, so it is relatively easily oxidized during long-term storage or storage in a high temperature and humid environment. It is known that this can happen.

Since developing solutions are usually stored in warehouses or outdoors, which are in poor conditions compared to denaturated photographic materials, it is desired that the developing solutions be stable even under such adverse conditions.

For ease of use, the developer for rapid access includes a type that can be used as is, as well as a concentrated type that is compressed as much as possible for convenience of transportation and cost considerations. In this case, the higher the amount of sulfite, the lower the concentration and the more earthy the pH, so it is not necessary to administer an amount of sulfite that maintains preservation. Therefore, another good method for preservation is needed.

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

However, we have found that this method cannot be considered preferable as a storage method for a developing solution in terms of oxygen permeability. This is because if the developer is encapsulated using the packaging material made of the synthetic organic polymer material described in the above-mentioned document and stored under high temperature and high humidity, the storage stability will not be good.

The reason for this is thought to be that under high humidity conditions, oxygen is easily permeated to 3A, and storage stability is deteriorated due to other factors. Therefore, packaging materials that are more suitable for storing developer solutions are desired.

[Purpose of the invention]

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

[Structure of the invention]

The object of the present invention is to provide (a) a developing agent, (b) a sulfite 0.
3 mol/l or more, and (c) a developer solution containing at least an alkaline agent that makes the developer pH 10 or more, in a method for storing a developer solution, in which the developer solution is stored in a container made of an organic polymer packaging material. the packaging material consists of at least two layers;
The organic polymer in the layer in contact with the developer among the plurality of layers is represented by the following general formula [a], and the organic polymer in at least one of the other layers is represented by the following general formula Cbl or [c]. This is achieved by a developer storage method characterized by the following. Furthermore, when the organic polymer in 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.

DI Tsushita Kouji General formula [a] 10C)! 2-C-+,.

In the formula, X and Y each represent a hydrogen atom, a /XOdene atom, a hydroxyl group, a carboxyl group, or an alkyl group, and! 1 is an integer greater than 100.

General formula [b1 +0C(CH2)pcON H(CH2)qN Hh In the formula, p and q each represent an integer of 1 to 12, and 1fi represents an integer of 100 or more.

General formula [C1 10N H(CH2)rCO-+7 where r represents an integer from 1 to 12,! represents an integer of 100 or more.

In the general formula [a], the alkyl group represented by , I] is preferably 10,
000 or less.

In the general formula [bl], m is preferably 10,000 or less, and in the general formula [e], 2 is preferably 10,000 or less.
,000 or less.

Specific examples of the compound represented by the general formula [a] include the following.

(a-1) 11→CI(2-C)l 2←-H (a-2) I4→CH2-CH2←-H (a-3) 1(-+CH2-C) ■ CI (a- 4) (α-5) (a-6) (a-7) The following can be mentioned as specific examples of the compound represented by the general formula [bl'c.

(b-1) HO+0C(CH2LCONo(CH2),,NH-)
--1-+HO10C (CH2), C0NH (CH2)
,N)(+7-H(b-3) HO+0C(C)(2)4CONH(CI-12)&N
H+-1-1(b-4) I(○+QC(CH2)2CON)l(C)l 2)6
Specific examples of the compound represented by NH-)-H general formula [e] include the following.

(c-],) 1-1-(-NH(CI-12), C0-)-OH(
c-2) 1(-fNH(CI-12)s C0-)--OH(
c-3) 1-(fNH(CI(2)=CO←O)-1(c
-4) 1-'+NH(CH2)' o coboH In the present invention, the organic polymer represented by the general formula [al, [1,] or [c1] can be obtained by monopolymerization, copolymerization or condensation polymerization from moamer. Can be easily synthesized. Note that in these general formulas, although terminal groups are not shown, those that occur during such polymerization reactions are included.

The thickness of each of the above-mentioned single layers constituting the organic polymer packaging material of the present invention is preferably in the range of 10 to 200 μl, and the total thickness of the laminated film is more preferably in the range of 30 to 600 μl. More preferably, the thickness of each single layer is 20 to 100 μl, and the total thickness of the laminated layers is 60 to 300 μl.
It should be in the μl range.

If the diameter of each of the above-mentioned single films constituting the organic polymer packaging material of the present invention is less than 10 μm, the storage stability of the developer will be poor and the strength will be low as a container for enclosing the developer.
It is preferable that the shoulder is 10μ or more, and 200μ1
If the packaging material is thicker than this, the flexibility of the packaging material is poor and it does not deform according to the amount of the developer inside, so air tends to accumulate in the dead space under the lid, resulting in poor storage stability of the developer.

The laminated organic polymer packaging material of the present invention preferably contains 10 to 200 μl of the compound represented by the general formula [al].
A thin film of a compound represented by the general formula [bl or [cl] with a thickness of preferably 10 to 200 μm is directly stacked on the 1V membrane film, or a thin film of the compound represented by the general formula [a
It can be obtained by stacking or laminating thin films of the compound represented by l as described above.

A container made of the packaging material of the present invention may be made of one layer of the packaging material, but it may be further covered with one or two layers of the packaging material, that is, made of two or three layers of the packaging material. The effect of the present invention can be further enhanced by a double or triple embodiment.

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

In a preferred embodiment of the present invention, the packaging material has a three-layer or four-layer structure, and among these layers, the innermost layer and the outermost layer contain organic polymers represented by the general formula [al]. Thus, an embodiment in which at least one organic polymer layer other than these two layers is represented by the general formula [bl or [C]] can be accelerated.

Examples of main developing agents that can be contained in the developer to which the method of the present invention is applied include the following.

(C1-1=CH)n-01- (Catecol, pyrogallol and its derivatives, and ascorbic acid are typical as type developers. , isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-nochlorohydroquinone,
2,5-methylhydroquinone, 2,3-nobromohydroquinone, 2゜5-nohydroxyaceto7/n, 2,5-methylhydroquinone, 2.5-')-
p-7enethylhydroquine, 2,5-nobenzoylaminohydroquine, catechol, 4-chloro f/
f-col, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-
Examples include pyrogallol, 4-(2'-hydroxybenzoyl)pyrogallol, and sodium ascorbate.

In addition, typical HO(CH=CH)n N H2 type developers include ortho and para 7-7phenol or ami-7virazolone, and 4-ami/7e/-
2-amino-4-chloro-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-ami/-
2-phenyl 7er/-ol, 3,4-noaminophenol, 3-methyl-4,6-tzami/7er/-er, 2,4-
Noaminoresorcinol, 2,4.6-)su7mino7er/-ol, N-methyl-p-7minophenol, N-β-
Examples include hydroxyethyl-p-7mino7-ethyl, 1)-hydroxyphenylami7acetic acid, 2-amino/naphthol, and the like.

For example, 4-7-7-2-methyl-N,N-diethylaniline, 2,4-diami/-N,N-diethylaniline, N-(4-ami7-3-methylphenyl)-morpholine, p-phenylenenoamine, 4-amino-N,N
-diethyl-3-hydroxyaniline, N , N , N
',N'-tetramethylbaraphenylenediamine,
4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-
N-(β-hydroxyethyl)-aniline, 4-ami/
-N-ethyl-(β-methoxyethyl)-3-methyl-
Aniline, 4-amino-3-methyl-N-ethyl-N-
(β-methylsulfonamidoethyl)-aniline, 4-
Ami/-N-butyl-N-γ-sulfobutyla:'Jn, 1-(4-7minophenyl)-pyrrolione, 6-amino-1-ethyl-1,2,3,4-tetrahydroquinone, 9-amino Examples of petrocyclic type developers include 1-phenyl-3-pyrazolidone and 1-phenyl-3-pyrazolidone.
-phenyl-4-7mi/-5-pyrazolone, 1-(p-
7mi/phenyl)-3-7mi/-2-pyrazoline, 1-
phenyl-3-methyl-4-ami/-5-pyrazolone,
Examples include 5-aminouracil.

Others: T, H, Noames The Theory of.
The Photographic Process 4th Edition (The Tl+
theory of the Photograpl+ic
Process+Fourtb Edition) No. 291-334 True and Journal of the American Chemical Society (Journal of
the American Chemical 5oc
iety) Volume 73, Page 3100 (1951) @
Developers such as those listed above can be effectively used in the present invention.

Even if these developers are used alone, 2. Although Fi1 or more may be combined, it is preferable to use two or more in combination.

Examples of the sulfite contained in the developer to which the method of the present invention is applied include those commonly used in developing solutions, such as sulfite, rum, potassium sulfite, and ammonium sulfite. The developer may contain hydroxylamine or a hydranoid compound as a preservative.

Examples of alkaline agents for raising the pH of the developer to which the method of the present invention is applied are 10 or higher, such as caustic alkalis (e.g., sodium hydroxide, potassium hydroxide, etc.), alkali carbonates (
Examples include sodium carbonate, potassium carbonate, etc.), amines, and other alkaline agents commonly used for development.

Other buffer agents (1) I] used in general black and white developers, Kuroiso development inhibitors such as brompotali, benzotriazole, etc. (development inhibitors, metal ion extraction agents such as ethylenediaminetetraacetic acid, methanol, ethyl alcohol, etc.) - Le,
Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin,
It is optional to add a hardening agent such as glyoxal, an ionic strength regulator such as sodium sulfate, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples. The technical scope of the present invention will be described in detail by the following examples.
However, the present invention is not limited to this, and a wide variety of implementations are possible.

〔Example〕

Preparation of photosensitive material for testing A silver halide photographic material was prepared according to Comparative Example 3 of Japanese Patent Publication No. 59-50976.

Preparation of developer Concentrated QA and B were prepared according to the following recipe.

Developer prescription (concentrated solution A) Pure water (ion exchange water) 150zf
Ethylenediaminetetraacetic acid disodium salt 2-tanoethylene glycol 50゜Sulfite 1'ffl Potassium (55% 14/v aqueous solution) 100z1
Potash Rum Carbonate 502 Hydroquinone 1525-Methylbenzotriazole 200B1-Phenyl-
5-Mercaptotetrazole Potassium hydroxide Potassium bromide in an amount to bring the pII of the working solution to 10.6
4.52 (Concentrate B) Pure water (ion-exchanged water) 311 Diethylene glycol 5ag ethyleneaminetetraacetic acid disodium salt 25zy acetic acid (90%
Aqueous solution) 0.3x15-nitroingsol

Preparation of Developer Storage Container Capacity 1 (package 7'' of layer structure and film thickness shown in Table 1 below)
Is it 8 yen? ll-5・,-,V bottom margin, strength''-I The above concentrated solution 101 is sealed in the above container and stored at high I amount and high humidity (1 out of the number of thermometer tests is 65℃, relative humidity 90 %
After storage for one week), a working solution was prepared, and changes in photographic performance were examined using the light-sensitive material.

Photographic performance was determined by exposing the sample to light through an optical sensitometric lens, and then developing it using an automatic development process using the developer formulation described above. A commercially available fixer for rapid access was used as the fixer.

Processing conditions Development: Fixing at 33°C for 20 seconds Washing at 30°C for 20 seconds Drying at 25°C for 20 seconds at 50"C The reciprocal of the exposure amount required to obtain .0 is expressed as a relative value of 100.The results are shown in Table 2. The developer sealed with the packaging material according to
It can be seen that there is little decrease in sensitivity even when stored under high temperature and high humidity conditions. From this, it is inferred that if the packaging material according to the present invention is used for double or triple packaging, the storage performance will be further improved.

〔Effect of the invention〕

By using the packaging material according to the present invention as a packaging material for a developer containing at least a developing agent, a sulfite of 0.3 mol/l or more, and an alkaline agent that makes the pi of the developer 10 or more, known packaging can be obtained. The storage stability of the developer is improved compared to the case where the material is used.

Claims (2)

[Claims] (1) A developer containing at least a developing agent, a sulfite of 0.3 mol/l or more, and an alkaline agent that makes the pH of the developer 10 or more, stored in a container made of organic polymer packaging material. In the storage method, the packaging material consists of at least two layers, the organic polymer in the layer in contact with the developer is represented by the following general formula [a], and at least one of the other layers
A method for preserving a developer, characterized in that the organic polymer of the layer is represented by the following general formula [b] or [c]. General formula [a] ▲ Numerical formula, chemical formula, table, etc. ▼ [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] −(OC(CH_2)_pCONH(CH_2)_qN
H)-_m [wherein p and q each represent an integer of 1 to 12, and m represents an integer of 100 or more. ] General formula [c] -(NH(CH_2)_rCO)-_l [In the formula, r represents an integer of 1 to 12, and l represents an integer of 100 or more. ] (2) Claim 1, characterized in that the other layer is composed of at least two layers, and the outermost organic polymer among these layers is represented by the general formula [a] above. How to store developer solution.