JPS6173147A - Conservative method of high ph developing solution - Google Patents

Abstract

PURPOSE:To conserve the titled developing solution with a good stability by storing it in a vessel made of a plastic casing material having a specific oxygen permeability and relative humidity. CONSTITUTION:The above described developing solution contg. a developing agent, >=0.40mol/(l) sulfite and an alkaline reagent sufficient to make the pH of the solution to >=11.5 may be stored in the vessel made of the plastic casing material having preferably <=25ml/(m<2>).atom.day (20 deg.C relative humidity 65%) oxygen permeability, thereby maintaining the stable photographic performance for a long period. For example, polyvinylidene chloride and 'nylon(R)' etc. are used as the above described plastic casing material.

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. The present invention relates to a method for preserving the developer obtained.

(Prior art) In the field of graphic arcs, a surface recognition system that exhibits photographic characteristics such as high contrast c-gamma (IO or higher) is required to reproduce continuous tone images using halftone images and to reproduce line drawings perfectly. It is.

Conventionally, a special developer called a Lith developer has been used for this purpose. Liss developer contains only hydroquinone as a developing agent, and is used in the form of an adduct with sulfite-based formaldehyde as a preservative so as not to inhibit its transferability and to keep the total concentration of free sulfite ions extremely low. be.

For this reason, Liss developer is extremely susceptible to air oxidation, so it is stored in containers separated into a part containing an alkaline agent and a neutral or acidic part containing developing chemicals and preservative gold. It is common practice to mix them in different proportions and use them for film processing.

In the graphic arc field, rapid access developers (gamma j to 7) are also used for stable and rapid processing systems, although they do not have as high a contrast as the Lith developer. The rapid access developer uses hydroquinone as a developing drug and usually/-phenyl-3-pyrazolidones or p-amine phenol compounds as an auxiliary developing drug, and has an extremely high concentration of sulfite as a preservative. Therefore, the developer is difficult to receive air oxidized gold, so there is no need to separate the developing agent and alkaline agent into separate parts, and the developer and alkaline agent dissolved together can be stored in a container and processed as is. Generally, it is used at times, or it is prepared in advance into a concentrated solution and diluted by adding water during conventional treatment. Rapid access acid developer solutions usually have a pH value of less than 0.Even if the packaging material of the container in which they are stored has high oxygen permeability, the stability of the stored developer solution is sufficient. It is maintained.

In recent years, in the field of graphic arts, a rapid, stable, and high-quality developing method has been disclosed that uses a stable developer solution with a high pH and a high sulfite concentration.

For example, US Pat. No. 221A, ≠01, ψ.

/At, ri 77, Dohiro, 144.7M-2, same a,
3it, 'yrt issue, II-, 272,604, ≠, 22/, 1j7, Dohiro, λ≠3,732, I
I, 26ri, Octopus No. 2 and JP-A Show RR-1ri O2ri 4
No. cJ etc. discloses a development processing method for quickly and stably producing high-contrast images mt using a high-pH developing solution with a high sulfite concentration. Even a developing solution with such a high pH has a high sulfite concentration. Provides stable photographic performance. However, even if such a high pH developer has a high sulfite concentration, if it is prepared and stored in a container made of a certain packaging material for a long period of one to two years before being used, As a result of gradual air oxidation, hydroquinone decreases and the pH of the solution increases.
jL out next.

Therefore, it is difficult to store the developing solution stably for a long period of time, giving different photographic performance depending on whether the storage period is long or short. It is known that the storage stability of the developer can be improved if the neutral or acidic part and the alkaline gold-containing part are stored separately. However, when such a method is used, a large amount of organic solvent is usually required due to the poor solubility of the developing agent. The use of a large amount of organic solvent is undesirable because it increases the cost of chemicals and increases the biological oxygen demand (B, O, DJ) of the developer.

Therefore, there is a strong demand for a method for stably storing the Tomodaka pH developer solution for a long period of time by coexisting the developing agent with an alkaline agent.

(Objective of the Invention) An object of the present invention is to provide a method for stably preserving a high pH developer containing a crude drug, a preservative, and an alkaline agent.

(Structure of the Invention) The object of the present invention is to remove oxygen from a solution containing a developing agent, a sulfite with an amount of O8 mol/l or more, and an alkali agent sufficient to make the liquid's pi (i//, 7 or more). Transparency! 0rrLl
/lrL2·atom-day IHA degree λOaC relative humidity 6j) or less) was achieved by storing in a container of plastic packaging material.

More preferably, the oxygen permeability is 21 mJ/TIL2・at
om・day (Temperature 20 oC1 relative (Matz %
) By storing the developer in a container made of NOFRASTIC packaging material, stable photographic performance can be obtained for long-term storage of the developer.

The method for measuring oxygen permeability is N, J.

02 permeatio of Calvano et al.
n of plastic container, M
Odern Packingtytr December issue l hong 3
~l Hirohiro! The method described on the page is used.

Plastic packaging materials with oxygen permeability of less than jOml/m2 atnm-day (temperature 20'C1 relative humidity 6!C) include, for example, polyvinylidene chloride, nylon,
Saponified ethylene-vinyl acetate copolymer (i?1 person-r
-C-ru), holivinyl alcohol (trade name Vinylon)
, polyvinyl chloride, aluminum foil laminated film, metal-deposited film such as aluminum, etc. can be used alone or in combination, and composites laminated to a substrate such as all-polyethylene or ethylene-vinyl acetate copolymer can be used. Film can also be used. The shapes of containers made using these plastic packaging materials include bottles, cubic types, and laminated pillow types. In the case of a bottle or cubic type, it can also be molded as a circular coextrusion laminated material using the above-mentioned materials with low oxygen permeability.

Among the above materials, polyvinylidene chloride, nylon, and ethylene/vinyl acetate copolymer compounds have low oxygen permeability, are strong when shaped into containers, and are difficult to process into containers due to their material characteristics. It is a particularly preferred plastic packaging material because it is easy to process.

There are no particular restrictions on the developing agent used in the developer used in the present invention, but it is preferable to use dihydroxybenzenes containing gold, as it is easy to obtain good halftone dot quality. A combination of enyl-3-pyrazolidones or a combination of fc-hydroxybenzenes and p-amine phenols may also be used.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, inopropylhydroquinone, methylhydroquinone, J,j-dichlorohydroquinone, 2. j-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, λ,t-dimethylhydroquinone 7, and hydroquinone is particularly preferred.

The developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention is /-722-3-pyrazolidone, l-7''C-nyl-hiro, ≠-dimethyl-3-pyrazolidone, /-722 Ru≠-Methyl-≠-human axymethyl-3-pyrazolidone, l-phenyl-≠,≠-dihydro#'/Mef-3-pyrazolidone, l-phenyl-y-methyl-3-pyrazolidone, /-p-amino Phenyl-≠, Hiro-dimethyl-3-pyrazolidone, /-p
-Tolyl-Hiroshi, ≠-dimethyl-3-pyrazolidone, and the like.

Examples of the p-amine phenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-cedroxyethyl)-p-aminophenol, N-(≠-hydroxyphenyl)glycine,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is usually 0.0! Mol/! Preferably, it is used in an amount of ˜O6 r mol/l. Further, when using a combination of dihydroxybenzenes and l-phenyl-3-pyrasolitones or hp-amino-phenols, the former f0.
01 mol/l, 0°! Mol/l. latter f0.06 mol/
It is preferable to use it in a scene of 1 or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfites are 0. It is preferably 0.2 mol/l or more, particularly 0.2 mol/l or more. Also, the upper limit is λ,! Preferably it is up to 7 mol/l.

The alkaline agents used to set 9H include sodium water mold, potassium hydroxide, and sodium barley.

Contains pH regulators and buffers such as charcoal potassium, tribasic sodium phosphate, and tribasic potassium phosphate.

It is the same as a general silver halide photographic developer except that it contains a developing agent, a sulfite of 0.4 C mol/It or more, and an alkaline agent with a pH of 3 or more. Additives used in addition to the above include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methylbenulf. , hexylene glycol, ethanol, methanol, and other organic solvents: l-phenyl-
mercapto compounds such as mercaptotetrazole, comercabutobenzimidazole, monosulfonic acid sodium salt, indazole compounds such as j-nitroindazole, penttriazole compounds such as methyl benzole, etc. It may contain an antifoggant or a black pepper inhibitor, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A No. 4-1062. It may also contain the amine compounds described in ≠≠.

The present invention will be explained in more detail with reference to Examples below.

Example 1 The following developer composition was melted into fj00 and when used, water j00
Add m1f and process as 11 working solution.

Developer Sodium ethylenediaminetetraacetic acid /, Of sodium hydroxide /j, Of tribasic potassium phosphate 7 hiro, O2 potassium sulfite
Ta o, oy3 noethylamino l-pro/ξ nor 10fN-methyl-p
-aminophenol//2 sulfate 0. If hydroquinone! 1. Of! Methylbenztriazole 0. ! ? λ-mercaptobenzimidazole sulfonic acid o, 2? Sodium bromide J, 0g Add water 0.11
(pH = tt, r) The above developer formulation was placed in a 1Ol container of the following φ type oxygen permeable plastic packaging material A%B%C%D.
A developing solution No. 1 was added and stored for one year, and water was added during development to use as a working solution, and changes in the pH of the developer and changes in photographic performance were investigated. The packaging materials, materials, average film thickness, and oxygen permeability used in this example are as follows.

Shape Material Packaging material Cubic type EVA packaging material NB Pillow type PE+EVA+E
VA (3-layer composition) Packaging material C pillow type EVAL (8)/N
Y/PE+ (2 layers I#) Packaging material D Cubic type NY/PE E(
Note) EVA・・・・・・・・・・・・・・・・・・
・・・・・・Polyethylene, acetic acid IPE・・・・・・・
・・・・・・Old・・・・・・・・・Polyethylene ■ EVAL ・・・・・・・・・・・・・・・Polyethylene, Acetic acid INY・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・Nylon EVAL/NY/
PE・・・・・・3 types of films are applied Oxygen permeability “F” Uniform HA Thickness ml/m 2° atom-day (temperature 20” (: relative humidity 2-day) 210μ
t00tILl50μ+100μ+100
μ 200m1 VA 20μ/lrμ/! j
μ+10μ j−7jμ//71μ
λO gonyl copolymer 2 minyl copolymer saponified product 2 composite film The film used to test the change in photographic performance is 0.3μ cubic silver iodobromide containing 2.1 mole iodide. Anhydro-j, j-cyclorotaethyl-3 in the emulsion
,3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt (sensitizing dye) f230
■/1 mole of silver, t-formyl-(2-44-(2-(2
, Hiro-di-t-pentylphenoxy)butyramide]phenyl)hydrazide@t, sy7 1 mole of silver, polyethylene glycol (molecular weight approximately 1ooo) 1 (3ooη/1 silver)
Mole addition, and further addition of 1-methylbenztriazole, ≠-hydroxy-6-methyl-/, J, Ja, 7-titrazaindene, dispersion of polyethyl acrylate, 2-hydroxy-/, 3. Add j-triazine sodium salt.

The coating solution thus prepared was coated on a polyethylene terephthalate film support with a coating weight of ≠ silver.

Of/TrL2, the gelatin coating powder was applied to an area of 2.197 m2 to form a film. The film thus obtained was passed through an exposure wedge for sensitometry.
Immediately after preparing the liquid solution with the above composition and packaging material A.
, stored in containers B, C, and D for t years, Jr.
Development processing was carried out at 0C for 30 seconds. The obtained sensitivity and pH value of the developer are shown in the following table.

In Table t, the sensitivity is determined when the concentration is 1. It is expressed relatively as the reciprocal of the amount of exposure required to obtain the amount of water.

As is clear from Table 1, packaging material A with a large amount of oxygen permeation,
In the case of B, if stored for t years, the sensitivity of the developer increases and p
The H value is also increasing. - It is clear that the containers using packaging materials C and D2, which have a low oxygen permeation rate and are made using the method invented by Rikki, are excellent, with almost no change in sensitivity and only a very slight change in pH.

Example 2 The following developing solution composition (I)' was dissolved at ≠oorrt, and the developer composition (■) was dissolved in 1 (to Oml, and water j00
In addition to rntf, the phenomenon is treated as the working solution 11.

Developer solution set 55t (Il Tetrasodium ethylenediaminetetraacetate /, Of potassium carbonate it, Of potassium hydroxide
/7,0? potassium bromide
2.0f potassium sulfite taQ, θ1
Hydroquinone λ3. ρ1!・Methylbenztriazole 0-0! f Add water and hiro00r
nl (pHit, 7t):) Toy liquid composition (II) j Nitroindazole di, θP? triethylene glycol, oJzy sodium hydroxide
l Add water toOtnl The above (11! Prescription of liquid composition (I)) Example 1
Same packaging material as in case A, B, C, Dr) #d 1 in container
073 current □ Stored in liquid gold for one year, and when processing current slag, removed current I.
# Add liquid composition fnl and water to use the liquid and investigate the changes in photographic performance of the developer.

Changes in photographic performance All tested films include 7 commercially available films.
A friend who uses Gillis contact film KUV-100f. This film was passed through an exposure wedge for sensitometry, and then the current falcon solution composition +11 was prepared immediately after and the packaging materials A and B were prepared.

1073 liquid i/year stored in 101 containers of C and D'vil-JJr'(:J(comparative development process in 17 seconds).

Here, the bottom of the development set (1) is prepared at the time of comparative development processing, and water is added to make the solution used. Table 2 shows the results obtained.
Shown below.

In Table 2, the sensitivity is determined by the developer composition (Il used immediately after preparation and the concentration/, j
It is expressed relatively as the reciprocal number t100 of the 'B element required to obtain .

As is clear from Table 2, packaging material A with high chromium permeability
, B, the sensitivity of the developer decreases when stored for one year. - In the case of containers using packaging materials C and Di with a smaller oxygen permeation rate, which are the method of Riki's invention, the change in sensitivity is almost excellent.

Claims (3)

[Claims] (1) Developing agent (2) Sulfite 0.40 mol/l or more (3) A developer containing at least enough alkaline agent to make the pH of the solution 11.5 or higher, with an oxygen permeability of 50ml/
m^2・atom・day (temperature 20℃ relative humidity 65%
1. A method for preserving a high pH developer for silver halide photographic materials, comprising storing it in a container made of plastic packaging material as described below.