JPS61102644A - Processing solution for silver complex salt diffusion transfer - Google Patents

Abstract

PURPOSE:To obtain processing characteristics small in dependence on processing conditions and stable for a long term by incorporating a specified alkaline agent and amino alcohol. CONSTITUTION:The processing soln. contains carbonate as an inorg. alkaline agent, and amino alcohol having a rhoKa of <=0.9 in an aq. 50% ethanol at 25 deg.C. It is preferable to add at least one kind of amino alcohol having a rhoKa of <9 and at least one kind of it having a rhoKa of >=9. Such amino alcohols higher and lower in rhoKa exhibit higher and lower rhoKa values to the rhoKa of carbonic acid in the processing soln. having absorbed it, respectively. Accordingly, while the processing soln. is fresh, the high buffer ability of Na2CO3 is complemented with the activity of the amino alcohol higher in rhoKa, and as the running processing progresses and the soln. absorbs CO2, main activation ability comes to depend mainly on the amino alcohol lower in rhoKa, thus permitting good characteristics to be obtained stably in a long-term running processing.

Description

[Detailed description of the invention] (A) Industrial application field The present invention relates to a treatment liquid for silver complex diffusion transfer.

CB) Prior art and its problems The principle of silver complex diffusion transfer method (hereinafter referred to as DTR method) is as follows.
It is described in U.S. Pat. No. 2,352,014, and there are many other patents and documents that are well known. That is, in the DTR process, silver complex salts are imagewise transferred by diffusion from a silver halide emulsion layer to an image-receiving layer, and they are converted into a silver image, often in the presence of physical development nuclei. For this purpose, an imagewise exposed silver halide emulsion layer is placed or brought into contact with an image-receiving layer in the presence of a developing agent and a silver halide solvent, and the unexposed silver halide is Convert to soluble silver complex salt. In the exposed portions of the silver halide emulsion layer, the silver halide is developed to silver, so that it is no longer understandable and therefore cannot diffuse. In the unexposed parts of the silver halide emulsion layer, the silver halide is converted to soluble silver complex salts, which are transferred to the receiver no.0DTR where they form a silver image, usually in the presence of development nuclei. The method has a wide range of applications, such as :fi, type reproduction, lithographic printing plate preparation, block material preparation, and instant photography.

Especially when it comes to reproducing documents or making block materials,
A negative material having a silver halide emulsion layer and a positive material having an image-receiving layer containing physical development nuclei are brought into close contact in a DTR processing solution that usually contains a silver complex salt forming agent to form a silver image on the image-receiving layer of the positive material. let

The silver image must be pure black or black with a bluish tinge, and must also have a sufficiently high density.

Furthermore, high contrast and sharpness and good image reproducibility are essential, and high transfer speed is desirable.

Moreover, it is necessary that the good quality of the positive material is not significantly dependent on the processing conditions (eg time, temperature).

From the principle of the DTR method described above, it can be easily inferred that the image forming process is greatly affected by processing conditions, load, processing temperature, processing speed, etc. It is well known in the world.

General specific examples of characteristic changes caused by changes in the processing environment in the DTR method, especially changes in processing temperature and changes in conveyance conditions, are listed below: 1) Sensitivity, tone, color tone, density (reflection density, transmission density) 2) In low temperature processing, contamination (due to the formation of fine silver colloid) is likely to occur on the image receiving sheet. 3) The ability to form minute images, e.g. fine lines or minute dots, may be affected by increases in processing temperature or transport speed. Until now, as a means to solve the above-mentioned problems, for example, Japanese Patent Application Laid-Open Nos. 48-93338, 1981-79445, 1982-157738, 1982-176036, Although many processing solutions have been proposed, such as those shown in 1982-72143, they have not yet been a comprehensively satisfactory method.The reason behind this is that the DTR method does not require chemical development, dissolution, diffusion, This is probably because it was thought to be difficult to control because it depends on a delicate balance with physical development.

Moreover, the above-mentioned changes in characteristics become more noticeable or may occur anew if processing g is continued to be used for a long period of time (referred to as running processing).

Generally, a DTR processing solution contains an alkaline agent, a silver oxide solvent, a preservative, and if necessary, a developing agent and other processing agents. Inorganic alkaline agents such as sodium, potassium hydroxide, and sodium phosphate have been preferably used; however, these inorganic alkaline agents have high activation ability and are therefore preferred while the processing solution is new. However, it has the disadvantage that the activation ability is rapidly reduced by running treatment.

(0 Purpose of the Invention The purpose of the present invention is to provide a processing solution for silver complex diffusion transfer that has very little dependence on changes in processing conditions and has good photographic properties, and that has improved running processability. It is to provide.

((9) Constitution of the Invention The above-mentioned object of the present invention is to provide a processing solution for silver complex diffusion transfer containing an inorganic alkaline agent and an amino alcohol, in which 5 carbonates and an amino alcohol are used as an inorganic alkaline agent.
Aqueous solution containing 0 IC amount % of ethanol (25°C) P at A
This was achieved by a processing solution for silver complex diffusion transfer characterized by containing an aminoalcohol having a Ka value of less than 9, or preferably an aminoalcohol having a yKa value of 9 or more.

The present invention will be explained in more detail below.

The use of amino alcohol in the DTR treatment liquid is also described in the above-mentioned patent specification and other patent specifications and is well known.

However, amino alcohols having an r K a of 9 or more have generally been used more often than amino alcohols having an r K a of less than 9 as defined above. That's P Ka 9
This is thought to be because the above amino alcohols have higher activation ability. In fact, even among amino alcohols with a pKa of 9 or more, sodium hydroxide and sodium phosphate have historically been used in relatively large amounts.

Although the present invention is not limited to speculation, the present invention may be better understood through the following explanation of the rationale. In other words, factors that can cause changes in the properties of a realistic TR treatment solution as the running process continues include, for example, a decrease in the treatment agent due to the sheet material, a change in composition, a decrease in pH, and the loss of water (and volatile treatment agents). Possible causes include concentration due to evaporation, decrease in pH due to absorption of carbon dioxide gas in the air, and oxidation of the developing agent. 0, the Ministry of the Invention found out that the effect of carbon dioxide absorption is extremely large, and as a result of intensive research into ways to solve the problem,
By combining at least one amino alcohol with a 1z Ka value of less than 9 and an amino alcohol with a Ka value of 9 or more as defined below and using a carbonate as an inorganic alkali agent, the treatment solution can be treated for a long period of time immediately after preparation of the treatment solution. We have found that there is very little dependence on the processing conditions up to the second coating process, and that better properties than ever before can be stably obtained. Amino alcohols and amino alcohols of 9 or more are
.

Treatment liquid that has absorbed carbon dioxide gas, white charcoal dR (a, oo,
) for the OF Ka value, respectively, the lower F Ka
It was confirmed through experiments that it exhibits a high pK a. Therefore, while the treatment solution is new, the treatment is carried out while supplementing the high vacuum capacity of sodium carbonate with the activity ability of the amino alcohol with a P Ka of 9 or higher, and the second treatment proceeds and the treatment solution absorbs carbon dioxide. As it is absorbed, the activation ability mainly depends on the amino alcohol with a pKa of less than 9. Amino alcohols having a yKa of 9 or higher may not need to be used.

The F Ka value of amino alcohol is, for example, [STTR
ILiTY 0ONSTANT8 0F META
L-ION OOMPLEXK8J (Spatial
publicatjon 417 (1964) and IEL25 (1971), THE June 25th
Published by Maruzen Co., Ltd.] and can be easily measured.

In the present invention, the pKa value is defined as one measured at 25°C in a mixed solvent of ethanol and water at a weight ratio of 50:50. Generally, the Ka value is slightly higher (about 0.2) than the pKa value in the above mixed solvent, and for example, the following relationship exists.

Furthermore, the pKac of aminoalcohol] generally shows a very high value in practical processing solutions containing various processing agents.

The amino alcohol used in the present invention is a primary, secondary or tertiary amine compound having at least one hydroxyalkyl group, particularly preferably a secondary or tertiary amine. Amino alcohols include compounds represented by general formula (A).

General formula (X and XI represent a frozen candy atom, a hydroxyl group, or an amino group.! and m are 0 or an integer of 1 or more, n is 1
(representing an integer of 0) or more) Specifically, ethanolamine, jetanolamine,
triethanolamine, diimprono(nolamine,
N-methylethanolamine, N-aminoethylethanolamine, N,N-diethylethanolamine, N,
N-dimethylethanolamine, N-methylgetanolamine, N-ethylgetanolamine, 3-aminoalcohol, 1-amino-propan-2-ol, 4
-aminoalcohol, 5-amino-pentan-1-ol, 3,3-iminocybrobanol, N-ethyl-2,
Examples include 2'-iminodiethanol.

In addition, the above-mentioned 2-amino-2-(hydroxymethyl)
Propane-1,3-diol and 2-amino/-2-methylpropane-1,3-diol can also be used.

Regarding the pKa value defined above, it can generally be said that an amino alcohol having one hydroxyalkyl group has i>Ka of 9 or higher, and an amino alcohol having t-2 or more hydroxyalkyl groups has a FKa of less than 9 ◇ Combination The difference in PK a value of the amine alcohol used should be 0.3 or more, preferably 0.5 or more. The molar ratio of the 7-minoalcohol having a Ka value of less than 9 and the 7-minoalcohol having a Ka value of 9 or more is preferably in the range of 2:8 to 8:2.

Carbonates as alkaline agents used in the present invention include sodium carbonate and potassium carbonate.

The amount of t used is preferably in the range of about 0.1 to about 0.6 mol per mol of the processing solution.

If necessary, an alkaline agent such as sodium hydroxide or sodium phosphate may be used in the treatment solution of the present invention. Furthermore, preservatives such as sodium sulfite, thickening agents such as carboxymethyl cellulose, hydroxyethyl cellulose, Fogging inhibitors such as potassium bromide, benzotriazole, silver halide solvents such as sodium thiosulfate, toning agents such as 1-phenyl-5-mercap)
- tetrazole, development modifiers such as polyoxyl-rukie compounds, quaternary ammonium salts, development nuclei such as those described in British Patent No. 1,001,558, and if necessary For example, hydroquinone, 1-phenyl-3-pyrazolidone, etc. are contained.

The pH of the processing solution is the pH that activates the main developing system, and the normal lO
~14. The optimum pH for a particular DTR method varies depending on the photographic element used, the desired image, the type and amount of various compounds used in the processing solution composition, processing conditions, etc. The conditions of the processing carried out, such as time, temperature, etc., will vary depending on individual factors, such as the components of the photographic element, the components of the processing liquid composition, etc., but are not limited.

The processing solution of the present invention is suitable for carrying out the 0DTR method, which is less dependent on changes in processing conditions and has a stable subsequent processing ability.
No. 1,012,476, No. 1.093,177, etc., a light-sensitive silver halide emulsion tm and/or an image-receiving layer, or other water-permeable colloid layer adjacent thereto. A developing agent is usually mixed into the film. Therefore, the processing solution used in the development step can be a so-called alkaline activating solution that does not contain a developing agent. In the present invention, it is preferably possible to use an alkaline activating solution.

In addition to the various metal compounds mentioned above, the processing solution of the present invention may contain other additives generally used in DTR processing solutions. consisting of at least one iron halide emulsion layer provided on n;
Generally silver halide ij converted to silver nitrate: 0.51~
3.517m” (D range 1i1111fmisufl.

In addition to this silver halide emulsion layer, auxiliary layers such as an intermediate undercoat layer, a protective layer, and a release layer may be provided as necessary.For example,
The negative material P+ used in the present invention is
34, No. 38-18135, etc., such as methyl cellulose, sodium salt of carboxymethyl cellulose, sodium alginate, etc., can be used as a coating layer for the silver halide emulsion layer to ensure uniform transfer. This layer should be thin so as not to effectively prevent or inhibit diffusion. Silver halide emulsion layers in negative materials and image-receiving layers in positive materials all contain hydrophilic colloids v! J-purchase, such as gelatin, gelatin fat conductor such as phthalated gelatin, carboxymethyl cellulose,
cellulose derivatives such as hydroxymethylcellulose,
Contains one or more hydrophilic polymer colloid substances such as dextrin, soluble starch, polyvinyl alcohol, and polystyrene sulfonic acid.

The silver halide emulsion consists of silver halides, such as silver chloride, silver bromide, silver chlorobromide, and iodide-containing compounds thereof, dispersed in the above-mentioned hydrophilic colloid. Silver halide emulsions can be sensitized in a variety of ways when they are manufactured or coated, e.g. by sodium thiosulfate, alkylthioureas, or by gold compounds, e.g. gold rhodium, gold chloride. The emulsion may also be chemically sensitized by methods well known in the art, such as by or a combination of both.
It is typically sensitized to a range of about 560 nm, but can also be panchromatically sensitized. Direct positive silver halide emulsions may also be used.

The silver halide emulsion layer and/or the image-receiving layer may contain any compound commonly used for carrying out the silver complex diffusion transfer method. Examples of metal halides include tetrazaindene and mercaptotetrazole. The coating agent may contain fog suppressants such as the like, coating aids such as saponin and polyalkylene oxides, hardeners such as formalin and chrome alum, and softening agents. The support used for the negative material or positive material may be any commonly used support, even if it contains a developing agent. It includes paper, glass,
Films such as cellulose acetate films, polyvinyl acetal films, polystyrene films, polyethylene terephthalate films, etc., metal supports coated on both sides with paper, and paper supports coated on one or both sides with an α-olefin, such as polyethylene, can also be used. The zero-positive material may contain physical development nuclei, such as l metal or its sulfide. One or more types of positive materials,
.

a substance in the layer that plays a prominent role in the formation of the diffusion transfer image;
For example, British Patent No. 561,875 and Belgian Patent No. 5
Zero positive materials may also include black toning agents such as those described in No. 502,525, such as l-phenyl-5-mercaptotetrazole.
It may also contain a fixing agent such as sodium thiosulfate in an amount of 17 m''. Materials] On one side of a 11 og/m paper support coated with polyethylene on both sides, an image-receiving layer consisting of PV material containing palladium sulfide cores, a processed product of ethylene 7/maleic anhydride co-heavy metal material, and gelatin was dried. 0 [Positive material B] A hardened gelatin image-receiving layer containing palladium sulfide nuclei was provided on a polyethylene terephthalate film to make a positive material. Material B was prepared ◎ [Negative material included] On the same paper support as the positive material, an undercoat layer containing carbon black to prevent swelling was provided, and on top of that, an undercoat layer containing carbon black with an average particle size of 0.3μ was applied. Silver chlorobromide (silver bromide 2 mol%) t-
A negative material was prepared by providing an ortho-sensitized gelatin silver halide emulsion layer containing 2.317 m'' in terms of silver nitrate.

[Processing liquid]

The following treatment solutions (1) to (1) were prepared (composition CI7)
(υ @ I attached the negative material to a normal plate-making camera, exposed the image, brought it into close contact with the positive material and B, and transferred the image. @ The transfer processor is a Mitsubishi Paper Mills variable conveyance speed.
0aF-12 (trade name) was used, and the treatment liquid temperature was arbitrarily set. The transfer time was 60 seconds. ◎ The document for image exposure was
(every 10-minutes), a reflective optical wedge is placed, and the exposure amount is controlled from the wedge of the transferred image.
The ability to form a microscopic surface source was evaluated based on the formation state of By changing the speed, the residence time of the negative material in the processor liquid was changed to 3 seconds, 6 seconds, and 9 seconds. After the set treatment, each treatment solution was allowed to age for 4 days in a carbon dioxide atmosphere with dry ice, and the treatment solution (all pH values were 1O92 at 20°C).
Transfer treatment was performed again and physical properties were evaluated.

Table 1 shows the processing conditions of 11.8 degrees Celsius and the evaluation of the coating/washing processability using the new solution.

(Left below) The processing solution 1 of the present invention not only provides high-density forgeries, but also is stable against changes in processing temperature, is free from contamination during low-temperature processing, and has good halftone color tone. Excellent ability to form minute images Example 2 The procedure of Example 1 was followed except that the amino alcohol in the processing solution I of Example 1 was as shown in Table 2 below. Results similar to those in Example 1 were obtained.

Example 3 [Negative material B] Negative material B was produced in the same manner as in Example 1 except that hydroquinone and phenidone were contained in the undercoat layer.

A test was conducted according to the method of Example 1 using the following treatment liquid.

The same results as in Example 1 were obtained.

1 (F) Effects of the Invention The treatment liquid of the present invention has a high buffering capacity of alkali carbonate and 7.
Due to the activity of minoalcohol, it is possible to obtain stable and good properties for a long period of time, and it also has excellent tolerance to changes in processing conditions.

One A0

Claims (2)

[Claims] (1) In a processing solution for silver complex diffusion transfer containing an inorganic alkaline agent and an amino alcohol, carbonate is used as the inorganic alkaline agent, and amino acid with a pKa value of less than 9 in an aqueous solution (25°C) containing 50% by weight of ethanol is used as the amino alcohol. The above-mentioned processing liquid is characterized in that it contains alcohol. (2) The processing liquid according to claim 1, which contains at least one amino alcohol having a pKa value of less than 9 and one having a pKa value of 9 or more.